text:
# Creating Annotation Tools with the Annotation Graph Toolkit

## 1. Introduction

Linguistic databases are widely used in the scientific study of language and in language-technology research and development. Many software tools have been developed to support the creation of annotated linguistic databases, and some of them are documented in \[Bird and Harrington, 2001\]. Bird and Liberman have developed a model for expressing the logical structure of linguistic annotations, and have demonstrated that it can encode a great variety of existing annotation types \[Bird and Liberman, 2001\]. An annotation graph is a directed acyclic graph where edges are labeled with fielded records, and nodes are (optionally) labeled with time offsets. Figure 1 shows an annotation graph for a fragment of the TIMIT corpus \[Garofolo et al., 1986\].

Annotation graphs have opened up new possibilities for creation, maintenance and search, and lead to new annotation tools with applicability across the text, audio and video modalities. Annotation graphs are also permitting existing annotation tools – each with large user-bases – to be made fully interoperable.

The Annotation Graph Toolkit (AGTK) is a collection of software supporting the development of annotation tools based on the annotation graph model. AGTK includes application programming interfaces for manipulating annotation graph data and for importing data from other formats, a database interface, wrappers for scripting languages, specialized graphical user interfaces for annotation tasks, and sample applications.

This paper is addressed to developers of linguistic annotation tools. We begin with a high-level overview of the tool architecture (§2), before presenting the most important features of the annotation graph library (§3), the file I/O library (§4), and their scripting language interfaces (§5). In §6 we discuss our approach to tool creation, involving rapid high-level programming in scripting languages, interfaced to stable and optimized C++ libraries. We describe our model of inter-component communication, and our approach to GUI design, in which we create many special-purpose tools that are maximally ergonomic for the task at hand. All software, interface definitions, configuration files and data samples are available under an open source license.

## 2. Architecture

Existing annotation tools are based on a two level model. The system we discuss in this paper is based on a three level model, in which annotation graphs provide a logical level independent of application and physical levels. This is the three-level model of modern database systems \[Abiteboul et al., 1995\] applied to linguistic databases in support of data independence, data reuse, and software integration. The application level represents special-purpose tools built on top of the general-purpose infrastructure at the logical level.

The toolkit is comprised of several components, structured according to the architecture shown in Figure 2. This model permits applications to abstract away from file format issues, and deal with annotations purely at the logical level, through the annotation graph API. Annotation tools provide graphical user interface components both for signal visualization and for annotation, and the communication between these components is handled by an extensible event language.

As with other recent architectures for language technologies, e.g. \[Allen et al., 2000\], the architecture consists of a set of loosely-coupled, heterogenous components that communicate with each other by exchanging messages. This design has three benefits. First, components can be implemented in the most opportune language, and wrappers can easily be added to legacy and third-party components. Second, message traffic can be logged to facilitate error diagnosis and to permit inter-component and human-computer interactions to be replayed and analyzed. Third, message passing permits the transport protocol to be separated from the communication content. The former is enforced by the infrastructure, while the latter is extremely flexible.

## 3. The Annotation Graph Library

The annotation graph library (libag) is implemented in C++,111The library has recently been ported to Java. and provides functions for creating, deleting, modifying and searching the following annotation graph objects: *AGSet*, *AG*, *Annotation*, *Anchor*, *Timeline*, *Signal*, *Feature* and *Metadata*. These objects are related to each other according to the object model shown in Figure 3. The various objects will be explained in more detail as we describe the API.

The annotation graph library also keeps indexes for the *Annotation*, *Anchor*, *Feature* and *Metadata* types so that searches can be done efficiently.

The API provides access to internal objects – signals, anchors, annotations, etc – through the use of identifier strings. The types of annotation graph identifiers include AGSetId, AGId, and AnnotationId.

### 3.1. The structure of annotation graph identifiers

All identifiers are represented as strings. The internal structure of an identifier can best be understood in terms of the object hierarchy in Figure 3. Annotation graph identifiers are *fully-qualified*: given an object identifier, all of the ancestor objects can be discovered simply by inspecting the identifier. For instance, an anchor "Timit:AG1:Anchor2" belongs to the annotation graph "Timit:AG1", which in turn belongs to the AGSet "Timit".

Internally, the annotation graph library maps these string identifiers to object references. A consequence of this design is that annotation graph objects can be referenced from scripting languages using human-readable names. The use of fully-qualified identifiers also reduces the risk of collision – the accidental re-use of the same identifier in different places – which can have unpredictable consequences.

### 3.2. Annotation graph API functions

This section explains some typical API functions. The complete IDL definition of the AG-API is available online \[http://www.ldc.upenn.edu/AG/\].

#### 3.2.1. AGSet and AG functions

An AGSet is an object which contains a set of annotation graphs. Typically, an AGSet corresponds to a corpus, but it might also correspond to a user-specified selection from a corpus, or to a selection spanning several different corpora. The first thing to do in working with annotation graphs is to create an AGSet object to hold them.

CreateAGSet. This creates an empty AGSet with a specified AGSetId, and returns the AGSetId:

```
AGSetId CreateAGSet(AGSetId agSetId);

```

Once an AGSet is created, Timelines, Signals, AGs, and then Annotations and Anchors can also be created. Certain functions can then be called on these data types, for example, to test for their existence or to delete them. An AGSet can be deleted by using DeleteAGSet. Its existence can be tested by using ExistsAGSet.

CreateAG. This creates an AG and returns the AGId; it throws an AGException if the id does not contain a valid AGSetId, or if the timeline does not exist:

```
AGSet CreateAG(Id id);
AGSet CreateAG(Id id, TimelineId timelineId);

```

The parameter id may be either an AGSetId or an AGId. If it is an AGSetId, an AGId will be assigned to the new AG. However, if it is an AGId, the library will try to use the supplied id. If this id is unavailable, it will assign a new AGId.

The timelineId is the id of the timeline with which the new AG will be associated. An AG can be created without being associated to any timeline.

#### 3.2.2. Timeline and Signal functions

A “timeline” is a collection of synchronized signals, such as separate audio and video recordings of the same event, or a multichannel recording of a conference call. The key defining property of a timeline is that the offsets into its signals are intertranslatable; any offsets into any one of the associated signals can be mapped to an offset into any of the others. Whenever multiple signals or channels are used in an annotation task, they are assigned to a distinct Signal object.222 An exception to this is the situation of a multichannel recording in which the different tracks are not discriminated in the annotation task; here they may be treated as a single Signal object. Multiple synchronized signals are grouped into a single Timeline object.

The functions CreateTimeline, ExistsTimeline and DeleteTimeline will now be explained.

CreateTimeline. This creates a new *Timeline* and returns the TimelineId:

```
TimelineId   CreateTimeline(Id id);

```

Id is AGSetId or TimelineId. In either case, the *AGSet* to which the *Timeline* belongs must already exist; otherwise an exception will be thrown. For example:

```
/* Create an AGSet with id "Timit" */
AGSetId agSetId = CreateAGSet("Timit");

/* Create a new timeline */
TimelineId timeline1 = CreateTimeline(agSetId);

/* Create another timeline */
TimelineId timeline2 =
             CreateTimeline("Timit:Timeline2");

/* The following causes an exception
since AGSet "CallHome" does not exist */
TimelineId timeline3 =
             CreateTimeline("CallHome");

/* The following also causes an exception */
TimelineId timeline4 =
             CreateTimeline("CallHome:Timeline2");

```

ExistsTimeline. This tests for the existence of the specified *Timeline*, and returns true if it exists and false otherwise:

```
boolean ExistsTimeline(TimelineId timelineId);

```

DeleteTimeline. This deletes the specified *Timeline* if it exists:

```
void DeleteTimeline(TimelineId timelineId);

```

CreateSignal. This creates a new signal and adds it to the timeline.

```
SignalId CreateSignal(Id id, URI uri,
  MimeClass mimeClass, MimeType mimeType,
  Encoding encoding, Unit unit, Track track);

```

The id argument might be TimelineId or SignalId. If it is a TimelineId, the library will generate a new SignalId. If it is a SignalId, the library will try the given id first, and if it’s taken, generate a new SignalId. If the id given is invalid, it throws an AGException.

The uri argument specifies a location where the signal is to be found. Applications may use this information to display and replay a signal. The mimeClass and mimeType arguments tell an application about the format of the signal, while the encoding argument specifies how samples are coded (e.g. mu-law). The unit argument specifies the sample rate of the signal; annotation applications may use this information to set the granularity of time coding and time alignment in a user interface. The track argument records which track of the signal file contains the signal. In this way, we can create two or more distinct Signal objects which reference different tracks of the same signal file.

GetSignals. This returns SignalIds of the *Signals* contained in the specified *Timeline*:

```
SignalIds GetSignals(TimelineId timelineId);

```

The SignalIds are separated by spaces.

#### 3.2.3. Annotation Functions

CreateAnnotation. This creates a new annotation:

```
AnnotationId CreateAnnotation(Id id,
                   AnchorId start, AnchorId end,
                   AnnotationType annotationType);

```

The id argument can be an AGId or an AnnotationId. If it is an AGId, an AnnotationId will be assigned to the new annotation. On the other hand, if it is an AnnotationId, the library will try to use the supplied id. If this id is unavailable, it will assign a new AnnotationId. The other arguments are as follows: *start* is the id of the start anchor; *end* is the id of the end anchor; *annotationType* is the type of the annotation.

CreateAnnotation returns the AnnotationId of the new annotation.

ExistsAnnotation. This returns true if the annotation exists:

```
bool ExistsAnnotation(AnnotationId annotationId);

```

DeleteAnnotation. This deletes an annotation:

```
void DeleteAnnotation(AnnotationId annotationId);

```

CopyAnnotation. This copies an existing annotation, with a new identifier assigned to the new annotation:

```
AnnotationId CopyAnnotation(AnnotationId annotationId);

```

SplitAnnotation. This splits an annotation into two, creating a new annotation with the same label data as the original one; returns Ids of both annotations.

```
AnnotationIds SplitAnnotation(AnnotationId annotationId);

```

NSplitAnnotation. This splits an annotation into N annotations, creating N-1 new annotations having the same label data as the original one; returns ids of all annotations, including the original one:

```
AnnotationIds NSplitAnnotation(
                AnnotationId annotationId, short N);

```

#### 3.2.4. Accessing Label Data

SetFeature. This sets the features of an annotation as well as the features of the metadata associated with *AGSets*, *AGs*, *Timelines* and *Signals*.

```
void SetFeature(Id id, FeatureName featureName,
                      FeatureValue featureValue);

```

The Id can be AnnotationId, AGSetId, AGId, TimelineId or SignalId. This is also true for other *Feature* functions, such as ExistsFeature, DeleteFeature, GetFeature, etc.

GetAnchorSet. This returns all the *Anchors* in a given *AG*.

```
AnchorIds GetAnchorSet(AGId agId)

```

GetAnchorSetByOffset. This returns all anchors with its offset in between offset-epsilon and offset+epsilon, inclusive. The default value for epsilon is 0.

```
AnchorIds GetAnchorSetByOffset(AGId agId,
            Offset offset, float epsilon=0);

```

GetAnchorSetNearestOffset. This returns all anchors at the nearest offset to the given offset:

```
AnchorIds GetAnchorSetNearestOffset(
            AGId agId, Offset offset);

```

#### 3.2.5. Accessing Annotations

GetIncomingAnnotationSet. This returns the incoming annotations of the specified anchor. The incoming annotations of anchor a are the annotations which end with anchor a:

```
AnnotationIds GetIncomingAnnotationSet(
                AnchorId anchorId);

```

GetOutgoingAnnotationSet. This returns the outgoing annotations of the specified anchor. The outgoing annotations of anchor a are the annotations which start with anchor a:

```
AnnotationIds GetOutgoingAnnotationSet(
                AnchorId anchorId);

```

For example, in the annotation graph shown in Figure 6, the incoming annotations of anchor 2 are a,b,c,d,e, and the outgoing annotations of anchor 2 are f,g,h.

GetAnnotationSetByOffset. This returns all annotations that overlap a particular offset.

```
AnnotationIds GetAnnotationSetByOffset(
                AGId agId, Offset offset);

```

GetAnnotationSeqByOffset. This returns all annotations sorted by start anchor offsets as the first sorting key, end anchor offsets as the second, and AnnotationIds as the third.

```
AnnotationIds GetAnnotationSeqByOffset(AGId agId);

```

```
AnnotationIds GetAnnotationSeqByOffset(
                AGId agId, Offset begin);

```

In this case, GetAnnotationSeqByOffset returns all the annotations with their start anchor offset greater than or equal to a specified offset, sorted by start anchor offsets as the first sorting key, end anchor offsets as the second, and AnnotationIds as the third.

```
AnnotationIds GetAnnotationSeqByOffset(
                AGId agId, Offset begin, Offset end);

```

In this case, GetAnnotationSeqByOffset returns returns all the annotations with the start anchor offset in between the specified offsets, sorted by start anchor offsets as the first sorting key, end anchor offsets as the second, and AnnotationIds as the third.

#### 3.2.6. XML save function

toXML. This returns a string in the ATLAS Level 0 XML format of the specified *AGSet* or *AG*:

```
string toXML(Id id);

```

The annotation graph library also provides functions to access a database server, for the persistent storage of annotations which may be shared by multiple annotators, as described by ?).

## 4. The File I/O Library

The I/O library is also implemented in C++. This section describes how the I/O classes are used to read native format files into annotation graphs and write them back.

Table 1 summarizes the formats which are currently supported by the I/O library.

There is one abstract class named agfio which declares the interface for the load and store methods, which are virtual functions. By inheriting the agfio class and implementing the load and store methods, each format will be a class with load and store methods. Loading or storing is done by creating an instance of a format class and calling the load or store method with the proper arguments.

As shown in Table 1, currently only AIF, LCF and TF formats can be stored.

## 5. Scripting Language Access to the APIs

The toolkit provides interfaces to the annotation graph libraries for the scripting languages Tcl and Python. To avoid having to manage object references across the Tcl/C and Python/C language interfaces and in the event language, all communication is via strings. These strings hold object identifiers, feature names and feature values. This section describes how to access the APIs from Tcl and Python.

For a Tcl program to access annotation graph functions, it must contain either of the following declarations:

```
package require ag

```

or

```
load ag_tcl.so
source ag.tcl

```

The following Tcl statement creates an annotation.

```
AG_CreateAnnotation $agId $a1 $a2 $ann_type

```

Note that the function name has the prefix AG\_. Newer versions of AGTK support the Tcl namespace as follows.

```
AG::CreateAnnotation $agId $a1 $a2 $ann_type

```

The argument $agId is an AG identifier, and the arguments $a1 and $a2 are Anchor identifiers. The argument $ann\_type is the type of the annotation (e.g. “word”).

Similarly, for a Python program, we need to import the AG module first:

```
import ag

```

The following code fragment creates an AGSet, a timeline, an AG, two anchors and an annotation.

```
agSetId = ag.CreateAGSet(’Test’)
timelineId = ag.CreateTimeline(agSetId)
agId = ag.CreateAG(agSetId, timelineId)
anc1 = ag.CreateAnchor(agId)
anc2 = ag.CreateAnchor(agId)
ann1 = ag.CreateAnnotation(agId, anc1, anc2, "Word")

```

The following fragment specifies features for a particular annotation, and prints the AIF representation to standard output.

```
ag.SetFeature(ann1, "English", "cat")
ag.SetFeature(ann1, "Japanese", "neko")
print ag.toXML(agId),

```

## 6. Building Annotation Tools with Tcl/Tk and Python

Most large-scale annotation projects must deal with multiple tools and formats. If all required tools were developed by a single project, and are used exactly as the original developers intended, there is usually no problem with interoperability. However, in 99% of the remaining cases, format translation and tool interoperability is a critical issue.

If annotation tools are created around a common architecture and a shared data model, these issues do not arise. New file formats are supported by writing a converter between the the format and the general-purpose data model. The sharing of components among different annotation tools is straightforward, and new applications can be developed quickly using existing components. New functionalities added to a component can be used by all existing tools which include that component.

The annotation graph library and the file I/O library provide the means to create, manipulate, read and write annotation graph data. In this section, we explain our approach to tool creation using these libraries as the core of the tool architecture.

All of our annotation tools are created using scripting languages having easy-to-use GUI libraries. This permits a rapid development cycle and easily customizable user interfaces. Tools are relatively small since much of the work is done by AGTK, and this small size and common data model mean that tool components are readily repurposable. We deliberately avoid the temptation to create general purpose annotation tools since each annotation task is idiosyncratic. Annotators work best when they use an interface which is maximally ergonomic for the peculiarities of the task, as compared with tools that include much irrelevant functionality and have an interface that is balanced for a wide variety of tasks.

This section describes the steps in creating a new special-purpose tool based on the general-purpose components provided by AGTK. It includes a discussion of inter-component communication, and of an example tool.

### 6.1. Building tools with Tcl/Tk

The Tk toolkit provides a graphical user-interface for Unix, Windows and Macintosh platforms. Some graphical user-interface components, called widgets, are provided with the Tcl/Tk standard distribution. For example the following fragment of Tcl/Tk code creates and displays a text widget:

```
set t [text .t]
pack $t

```

Other GUI components, such as buttons, menubars and canvases, come standard with Tk. In addition, open-source GUI components and extensions are developed and distributed by various developers around the world. Provides pointers to such software are provided at \[http://dev.scriptics.com\].

### 6.2. Building tools with Python

Python has become very popular as a scripting language. Python provides an object-oriented programming framework, and is easy to learn. A GUI package called Tkinter \[Grayson, 2000\] based on the Tk toolkit is included in the standard Python distribution. Tkinter provides class definitions for the standard widgets included in Tk. In addition, it is relatively easy to write a Tkinter class for a third-party Tk widget that is not directly supported by Tkinter.

The following segment of Python code creates and displays a Tk text widget.

```
from Tkinter import *
root = Tk()
t = Text(root)
t.pack
root.mainloop()

```

### 6.3. The inter-component communication model

An annotation tool built with the Annotation Graph Toolkit will consist of several major components, including: (i) a main program (script); (ii) an annotation/transcription component in which the user would enter annotations and transcriptions, and (iii) a signal display component giving access to recorded digital signals, such as speech waveforms. Typically, annotation/transcription components and waveform display components are reused by different specialized annotation tools. To create a new annotation tool, the developer writes a main program using the right selection of widgets and provides callback functions to handle widget events.

Events are passed around among components so that necessary tasks can be performed within each component. Consider the following example. Suppose that the user already has an annotation assigned to a specific region in the signal. He/she now wants to assign new start and end offsets for the signal to the annotation. Suppose the keyboard input *Control-g*, in the waveform component is assigned to such a task. When the user hits *Control-g* while there is a newly highlighted region in the waveform, this information (*event*) needs to be passed to the main program, and then to the annotation/transcription component and the annotation graph library. This propagation of event information is illustrated in Figure 7.

The event *SetRegion* is generated in the waveform component and passed to the main program with the two parameters, the start time and the end time. Then, the main program sends *SetRegion* to the transcription component so that the start and end offsets can be updated in the transcription component. Also, the main program uses the annotation graph function *SetAnchorOffset* to update the internal representation of the annotation graph data. Table 2 shows a list of typical events passed around in this manner.

These events and their necessary arguments are passed as associative arrays (e.g., Tcl arrays and Python dictionaries). These arrays are passed to event handlers defined in the recipients.

### 6.4. GUI design

A critical aspect of designing a successful annotation tool is to make it highly ergonomic for the particular annotation task. Writing a tool in a scripting language makes it easy to experiment and change various aspects of a user interface, and facilitates “power users” who can tweak the code to help streamline their work.

Where possible, our tools use simple keybindings that work in multiple contexts, making it easy for users to focus on the annotation task instead of having to hunt for obscure key combinations. In the MultiTrans annotation tool, a tool based on AGTK, the *Return* key is active in multiple contexts. If a new region in the waveform display is chosen (i.e., highlighted), pressing the *Return* key will create and insert a new annotation into the transcription display. If an existing annotation in the transcription display is chosen, its corresponding region in the waveform is highlighted. A single mouse-button click in the highlighted region will set a point. If the *Return* key is pressed then, it will split the annotation and the region. Figure 8 and Figure 9 show before and after split, respectively.

If the *Return* key is pressed during a playback, it will set an anchor point. When the playback of speech is begun, the user may press the *Return* key to insert an anchor in the current channel. When *Return* is pressed a small black bar will appear below the waveform (Figure 10). This designates the current starting position of the annotation. When *Return* is pressed a second time the end anchor for the annotation is inserted and the annotation is created.

All these different actions have a common theme, namely to “create” something. This heavy re-use of a keybinding requires a little more effort in the coding process, but we have found that it makes the annotation process faster and easier. Using scripting languages, it is very easy to experiment with the user interface in this way.

### 6.5. Audio and video display using third-party software: WaveSurfer and QuickTime

WaveSurfer \[Sjölander and Beskow, 2000\] was developed by Kåre Sjölander and Jonas Beskow of KTH as a tool for displaying and manipulating sound files. WaveSurfer uses Snack \[Sjölander, 2000\] as its signal processing module. Both packages are distributed under an open source license. WaveSurfer is written in Tcl/Tk and its widget, called *wsurf*, can be embedded in an application written in Tcl/Tk. A Python interface has also been developed. This makes WaveSurfer an excellent component to use with AGTK.

QuickTime Tcl is another component that can be used with AGTK. QuickTime Tcl requires the QuickTime player created by Apple Corporation. Currently, no UNIX version of QuickTime player is provided by Apple.

### 6.6. Embedding a third-party Tk widget in Python

Tkinter provides class definitions only for the original Tk widgets. However, it is relatively easy to write an extension of Tkinter for a third-party Tk widget. For example, AGTK includes a Python/Tkinter class definition for the Wsurf widget. The class *Wsurf* covers the Wsurf API. The class *agWsurf*, which is a subclass of *Wsurf*, provides methods specific to the tasks required by the tools we create.

### 6.7. A Tk table widget

AGTK comes with a table annotation component called agTable (or, ag-table as originally called in the Tcl version). The agTable component is based on TkTable written by Jeffrey Hobbs, et. al. \[http://sourceforge.net/projects/tktable/\].

### 6.8. Putting it all together: the case of TableTrans

Now that we have seen the major components of AGTK, we can examine how to build an annotation tool using these components. As an example, we will examine an annotation tool called TableTrans (Figure 11). TableTrans is a spreadsheet-style annotation tool that uses the components we have described in this paper.

TableTrans consists of three major components: (i) the main script, *agTableTrans*, (ii) the table component, *agTable*, and (iii) the waveform display component, *agWsurf*. Here we will look at two common operations: pressing the *Return* key in the table to insert a new annotation, and pressing the *Control-d* key combination in the table to delete the highlighted annotation.

The keybindings for *Return* and *Control-d* are already defined in the agTable component. The operations above pass the events *CreateAnnotation* and *DeleteAnnotation* to the main script, respectively. A callback function (*agTableEvent*) is defined in the main script. When the *Return* key is pressed, the table component sends the event *CreateAnnotation* to the main script. The callback function in the main script then performs the following tasks:

First, using the start and end offsets of the current region stored in the main script, it calls the annotation graph function *CreateAnchor* twice to create the start anchor and the end anchor:

```
a1 = ag.CreateAnchor(self._AGName)
ag.SetAnchorOffset(a1, self._currentStartPosition)
a2 = ag.CreateAnchor(self._AGName)
ag.SetAnchorOffset(a2, self._currentEndPosition)

```

Second, it calls the annotation graph function *CreateAnnotation* using the start and end anchors:

```
id = ag.CreateAnnotation(self._AGName,
                            a1, a2, annotationType)

```

This function returns the annotation identifier. Finally, the program returns the new identifier, along with the start and end offsets, to the table component. The table component inserts a new row using the annotation identifier and the start and end offsets.

Similarly when the *Control-d* key combination is pressed, the table component sends the event *DeleteAnnotation* to the main script together with the annotation identifier of the highlighted row. The callback function in the main script performs the following command, where dictionary *event* contains the event message.

```
ag.DeleteAnnotation(event[’AnnotationId’])

```

Then, the table component can remove the highlighted row from its table. Figure 12 shows the components of TableTrans and their relationships.

## 7. Conclusion

This paper has described a new toolkit, AGTK, which supports rapid development of linguistic annotation software. AGTK is being used for annotation projects at the Linguistic Data Consortium \[www.ldc.upenn.edu\]. The toolkit is available for download at \[http://www.sourceforge.net/projects/agtk/\]. For news and updates, please visit \[http://www.ldc.upenn.edu/AG/\].

Existing third-party tools, namely Emu and Transcriber \[Cassidy and Harrington, 2001, Barras et al., 2001\], are being migrated to AGTK. They will share the same internal data model and relational storage model, while keeping their distinctive user interfaces and file formats. Once these ports have been completed, we will have a shared library of user interfaces to complement the AG and file I/O libraries. We hope that these shared libraries will continue to grow as members of the wider community contribute I/O and GUI components to AGTK.

In future work, we hope to develop more applications for annotation in other areas, possibly including: sociolinguistics, conversational analysis, sign and gesture, discourse and dialogue. On the technical side, we hope to add interfaces to video widgets on all platforms, and to support data entry for extended-Roman and non-Roman scripts.

## Acknowledgements

This material is based upon work supported by the National Science Foundation under Grant Nos. 9978056, 9980009 (Talkbank). The authors are grateful to Claude Barras, Steve Cassidy, Mark Liberman and many others for discussions on the material presented here.


format: text

text:
# Self-trapped states and the related luminescence in PbCl2 crystals

## I INTRODUCTION

Electronic excited states relax into self-trapped (ST) states in solids where electrons strongly interact with acoustic phonons. Y. Toyozawa (1986) The structure of ST states has been extensively examined with electron-spin-resonance (ESR) technique in ionic crystals. K. S. Song and R. T. Williams (1993); R. H. Silsbee (1972) The annihilation of the ST states often induces photons due to electron-hole ($`e`$-$`h`$) recombination via electric dipole transition. Therefore, luminescence study is another effective technique to investigate the ST states in high-efficient luminescent materials. Comprehensive study with ESR technique and luminescence spectroscopy is often powerful enough to clarify the ST states and the correlation with luminescence.

Localized states of excited electrons and holes in PbCl2 crystals have been studied with ESR technique for the past few decades. In the early stage around 1970, the localized states induced by ultraviolet (UV) light irradiation at 80 K were observed around $`g2`$ (Refs. J. Arends and J. F. Verwey, 1967; W. C. De Gruijter and J. Kerssen, 1972; J. Kerssen et al., 1973). Figure 1 shows ESR signals photoinduced at 80 K; a set of five resonances around $`g2`$ was named as “A signal” W. C. De Gruijter and J. Kerssen (1972) and is enlarged in the inset. In addition, the ESR signals after x-ray irradiation at 10 K were also reported around $`g2`$, and were named as “B signal” and “C signal.” W. C. De Gruijter and J. Kerssen (1972) Though some trials were performed, J. Arends and J. F. Verwey (1967); W. C. De Gruijter and J. Kerssen (1972); J. Kerssen et al. (1973) the localized state responsible for the A signal has been disputable P. G. Baranov and J. Rosa (1990) and the origins of the B and C signals have not been identified yet. The next advance was reported by Nistor et alS. V. Nistor et al. (1993) and Hirota et alT. Hirota et al. (1993) in 1993; self-trapped electrons (STEL’s) induced by x-ray S. V. Nistor et al. (1993) and $`\gamma `$-ray T. Hirota et al. (1993) irradiation at 80 K were observed and found to be dimer-molecular Pb23+ centers. The ESR spectrum of Pb23+ is also presented in Fig. 1.

Localized states in PbF2 (Ref. M. Nishi et al., 1977) and PbBr2 (Ref. M. Iwanaga et al., 2002) have been revealed with ESR technique. In PbF2, only holes get self-trapped and form Pb3+ centers. M. Nishi et al. (1977) On the other hand, both electrons and holes get self-trapped in PbBr2, and form electron centers of Pb23+ and hole centers of Br2-, respectively. M. Iwanaga et al. (2002) The configurations of self-trapped holes (STH’s) are different between PbF2 and PbBr2. The difference is qualitatively explained by the components at the top of the valence bands; the $`6s`$ states of Pb2+ are the main component in PbF2, while the $`4p`$ states of Br- mainly constitute the valence band in PbBr2 (Ref. M. Fujita et al., 2000). According to the cluster calculation M. Fujita et al. (2000) for PbCl2, the top of the valence band is composed of about half-and-half Pb2+ ($`6s`$) and Cl- ($`3p`$). Therefore, the structure of localized hole centers in PbCl2 is significant to clarify the relation of hole-relaxation dynamics with the electronic-band structure in PbCl2 and to understand the relation in lead halides comprehensively.

Luminescence in PbCl2 has been studied in parallel to the ESR. The intense photoluminescence (PL) at low temperatures below 10 K was classified to UV-PL band at 3.8 eV, blue-PL band at 2.8 eV, and blue-green (BG) PL band at 2.5 eV. W. C. De Gruijter and J. Kerssen (1972); W. C. De Gruijter and T. Bokx (1973); G. Liidja and Vl. Plekhanov (1973) The UV-PL and the blue-PL bands are mainly induced under one-photon excitation into the exciton band, and the BG-PL band is dominantly induced under excitation into the energy region higher than the lowest exciton. 111Another PL band at 1.8–1.9 eV was reported. Because it is mainly induced under excitation into the low-energy range of the fundamental absorption including exciton absorption (Refs. W. C. De Gruijter and J. Kerssen, 1972; W. C. De Gruijter and T. Bokx, 1973 and M. Kitaura and H. Nakagawa, 2001), the PL band is unlikely to be intrinsic PL. Therefore, the PL band is not discussed in this paper. As the origins of the UV-PL band at 3.76 eV and the blue-PL band at 2.88 eV, the self-trapped excitons (STE’s) with the configuration of (Pb$`{}_{}{}^{+}+`$ hole) were proposed, and the origin of the BG-PL band was attributed to the STE’s of (Pb2$`{}_{}{}^{3+}+`$ hole). M. Kitaura et al. (2000); M. Kitaura and H. Nakagawa (2001); S. V. Nistor et al. (2000) The models claim that the lowest excitons and free $`e`$-$`h`$ pairs relax into different localized states. However, the Pb+ centers in PbCl2 have not been reported. Another interpretation on the PL bands was recently proposed; V. Babin et al. (2002) it declares that the UV-PL and blue-PL bands come from the STE’s of (Pb2$`{}_{}{}^{3+}+`$ hole) and the BG-PL band originates from the tunneling recombination of the pairs of a STEL of Pb23+ and a STH of Cl2-. On the other hand, another PL study M. Iwanaga et al. (2001) has shown that the PL below 10 K under two-photon excitation into the exciton band is dominantly composed of the BG-PL band, and the intensity of the UV-PL band heavily saturates such that $`I_{\mathrm{UV}}I^{\mathrm{\hspace{0.17em}0.6}}`$ where $`I`$ is intensity of incident light. The results imply that, under the bulk excitation like two-photon excitation, the relaxed states of $`e`$-$`h`$ pairs are independent of the excitation energy and yield the BG-PL band. Consequently, it is possible enough to explain that the lowest excitons created under one-photon excitation are captured by surface defects and result in the UV-PL and the blue-PL bands. Thus, the origins of PL bands are still disputable.

Excitons in PbBr2 crystals, which belong to the same crystallographic group R. W. G. Wyckoff (1963) with PbCl2 and have similar electronic-band structures, A. F. Malysheva and V. G. Plekhanov (1973); A. J. H. Eijkelenkamp and K. Vos (1976); J. Kanbe et al. (1977); M. Fujita et al. (2000) undergo uncommon relaxation; M. Iwanaga et al. (2000) they spontaneously dissociate and relax into spatially-separated STEL’s and STH’s. The recent ESR study M. Iwanaga et al. (2002) supports the relaxed state of excitons structurally. A similar relaxation in PbCl2 has been pointed out, M. Iwanaga et al. (2001) but the structures of the localized states have not been explored fully as already described.

We have comprehensively examined the localized states of photoinduced $`e`$-$`h`$ pairs and PL properties in a wide temperature range of 5–200 K. As a result, the localized states of holes at low temperatures below 70 K have been found to form STH centers of Pb3+; the structure of STH’s is different from that inferred from the ESR spectrum at 80 K as shown in Fig. 1 and from the recent study on PbBr2 (Ref. M. Iwanaga et al., 2002). We present the low-temperature ESR signals photoinduced below 10 K in Sec. III.1 and the PL properties in Sec. III.2. The STH’s are analyzed with spin Hamiltonian in Sec. IV.1. We discuss the correlation between ESR signals and PL in Sec. IV.2, the origin of the A signal in Sec. IV.3, and the relaxation dynamics of $`e`$-$`h`$ pairs in comparison with PbBr2 in Sec. IV.4.

## II EXPERIMENTS

Single crystal of PbCl2 was grown with the Bridgman technique from 99.999% powder. The crystal of orthorhombic D$`{}_{}{}^{16}{}_{2h}{}^{}`$ (Ref. R. W. G. Wyckoff, 1963) was cut in the size of 3$`\times `$3$`\times `$3 mm3 along the right-angled crystallographic $`a,b`$, and $`c`$ axes.

The sample was photoirradiated with the second harmonics (pulsed 120-fs-width, 1-kHz, and 3.10-eV light) generated from a regeneratively amplified Ti:sapphire laser; average power of the incident light was about 20 mW$`/`$cm2 on the sample surface. The incident photons induce two-photon interband transition, create $`e`$-$`h`$ pairs almost uniformly in the crystal, and produce measurable ESR signals within one minute. The samples were typically photoirradiated for five minutes. The irradiated sample was measured below 12 K with ordinary ESR technique in X-band range; resonant microwave frequency was 9.400$`(\pm 0.004)`$ GHz. The details of ESR and thermoluminescence (TL) measurements were previously reported in Ref. M. Iwanaga et al., 2002. Raising- and lowering-rates of temperature in measuring TL were 0.5 K$`/`$s. In pulse-annealing measurement, the sample was kept for about one second at annealing temperature.

PL was induced with the second harmonics (pulsed 5-ns-width, 10-Hz, and 2.33-eV light) generated from a Nd:YAG (yttrium aluminum garnet) laser; the incident light causes exciton-resonant two-photon excitation. The PL properties are essentially the same as those induced under one-photon excitation with UV light ($`\mathrm{}\omega `$4.8 eV). The PL was detected with an intensified CCD camera with a grating monochromator, and time-resolved PL spectra were measured by gating the CCD camera; the temporal resolution was 5 ns.

## III EXPERIMENTAL RESULTS

### III.1 ESR Spectra and thermoluminescence

Figure 2 shows typical ESR spectrum measured at 7 K after photoirradiation at 6 K; the ESR signals at 326, 522, 1400, and 1480 mT are readily induced together, while the signal at 1180 mT appears even in measuring empty capillary. Therefore, as reported in Ref. H. Kon, 1973, the signal at 1180 mT is ascribed to oxygen molecules in the capillary. The photoinduced four signals show similar thermal profile; besides, they saturate for microwave power higher than 0.01 mW below 7 K, while keep linear response up to 0.1 mW at 10 K. Consequently, the four signals are ascribed to the same origin. The intense ESR signal at 326 mT, which is enlarged in the inset, consists of one broad resonance with 6-mT width; the structure differs from the fivefold split A signal in Fig. 1. The signals at 326 and 522 mT are almost independent of rotation angles. Though the two signals around 1400 mT depend on rotation angles, they degenerate when the magnetic field vector is parallel to the crystallographic axes. The reason for the split and the rotation-angle dependence is discussed in Sec. IV.1. The intense line at 326 mT was induced by x-ray irradiation at 10 K and was named as C signal in Ref. W. C. De Gruijter and J. Kerssen, 1972. The small signal at 336 mT in the inset of Fig. 2 is the B signal named in Ref. W. C. De Gruijter and J. Kerssen, 1972; it is far weaker than the C signal and hardly depends on rotation angles. From now on, we focus on the main signals of the A, the C, and the satellite signals.

Except for 1180-mT resonance, the ESR spectrum in Fig. 2 is very similar to that of Pb3+ in KCl:Pb; D. Schoemaker and J. L. Kolopus (1970) therefore, the ESR signals in Fig. 2 are ascribed to hole centers of Pb3+. The hole centers are analyzed with spin Hamiltonian and are compared with Pb3+ centers in other host crystals in Sec. IV.1.

Figure 3 displays the ESR spectra measured at 9 K after photoirradiation at 8, 60, 70, 80 and 90 K. A sequence of the spectra was measured by carrying out the photoirradiation and the ESR-data taking alternately. The ESR spectra after irradiation at 8–50 K are essentially the same in shape. At 60 K, Pb23+ signals become prominent, and the signals around 330 mT are composed of Pb3+ signals and other split signals at 60–80 K. The Pb3+ signals are eventually replaced by the A signal at 90 K.

Figure 4 presents ESR spectrum (lower) after photoirradiation at 10 K, namely, before pulse annealing and ESR spectrum (upper) after pulse annealing at 100 K. Both spectra were measured at 12 K. The ESR spectrum before pulse annealing has the two prominent signals at 326 and 522 mT, which come from Pb3+ centers. In the spectrum after pulse annealing, the signals from STEL centers of Pb23+ appear around 460 mT, the A signal is observed around 330 mT, and the residual signal from Pb3+ centers is still detected in the low-magnetic-field side of the A signal.

Figure 5 shows TL-growth curve (solid line) and the intensity of ESR signals in Fig. 3 (open and closed circles and cross). TL is observed strongly at 60–85 K under the condition of raising temperature at 0.5 K$`/`$s. The TL spectrum in the temperature range is in agreement with the BG-PL spectrum.

In a previous TL experiment, M. Kitaura et al. (2000) TL-growth curve measured with raising temperature at 0.1 K$`/`$s shows two discrete peaks at 51 and 74 K. The difference probably results from the temperature-rising rate; the rising rate in the previous report is slower than that in our measurement. The discrete peaks suggest the two different thermal activation in 50–80 K. The two thermal transfers were assigned to hole activation in Ref. M. Kitaura et al., 2000. We discuss the activated carriers in Sec. IV.2.

### III.2 Photoluminescence

Figure 6 presents PL spectra under exciton-resonant two-photon excitation at 4.66 eV. The PL spectra at 6–70 K are peaked at 2.52 eV and almost invariant in shape. Above 70 K, the PL spectrum begins to move toward high-energy side, and the peak reaches 2.7 eV at 100 K. In the range above 100 K, low-energy PL around 2 eV relatively increases with raising temperature, and finally the PL spectrum consists of broad PL bands at 150 K. The thermal behavior of PL induced under one-photon excitation into the fundamental absorption region ($`\mathrm{}\omega 4.8`$ eV) is the same as that in Fig. 6.

Figure 7 shows PL spectra (solid line) and time-resolved PL (TRPL) spectra (dashed and dotted lines) under two-photon excitation at 4.66 eV, measured at 6, 75, and 90 K. The dashed line at 6 K represents the BG-PL band at 2.50 eV; the spectrum is obtained by measuring the PL over 1–99 ms, that is, by gating the CCD camera with 1-ms delay and 98-ms width. The BG-PL band decays phosphorescently; the intensity $`I(t)`$ is well described by $`I(t)=(K/t)[1\mathrm{exp}(t/\tau )]`$ where $`K`$ is a proportionality constant and $`\tau =100`$ $`\mu `$s. M. Iwanaga et al. (2001) The rest of the PL at 6 K is the PL band at 2.66 eV (arrow) and decays single-exponentially with 5.0 $`\mu `$s. This blue PL band is different from the blue PL band at 2.88 eV mentioned in Sec. I; the blue PL band at 2.88 eV is not induced under the present excitation. The PL spectra at 75 and 90 K are spectrally resolved with the TRPL spectra peaked at 2.79 eV (arrow). The blue PL band at 2.79 eV decays single-exponentially with 2.6 $`\mu `$s at 75 K. Thus, the relative increase of the blue PL band results in the apparent high-energy shift of the PL spectrum in Fig. 6.

PL intensity integrated over 2.0–3.2 eV at 6–200 K is plotted against temperature in Fig. 8; time-integrated PL intensity over 0–99 ms is represented with cross, and TRPL intensity over 1–99 ms with closed circle. PL intensity keeps almost constant below 50 K and increases in 50–70 K. The increase is coincident with TL growth (dotted line), and the peaks of PL and TRPL intensity are located at about 80 K. Because the TRPL intensity corresponds to the phosphorescent component of PL, the increase of the PL intensity is ascribed to that of the phosphorescent BG-PL. Indeed, PL at 75 K decays in proportional to $`t^1`$ for $`t1`$ ms. The TRPL intensity decreases in 80–100 K and is hardly observed above 100 K. The TRPL quenching is also coincident with the high-energy shift due to the relative increase of the blue PL band at 2.79 eV as shown in Fig. 7. Thus, the phosphorescent BG-PL band is induced below 100 K. Above 100 K, the blue PL band and other PL band around 2 eV are dominantly induced and are finally quenched around 200 K.

## IV DISCUSSION

### IV.1 Spin-Hamiltonian analysis of self-trapping hole centers

The ESR signals at 326, 522, and about 1400 mT in Fig. 2 show the same temperature profile and the intensity ratio $`(326\text{ mT}):(522\text{ mT}+1400\text{ mT})=8:2`$. The ratio is consistent with the isotope ratio of Pb ions; they have two isotope series such as $`I=0`$ and $`1/2`$, and the natural ratio is about $`8:2`$. If the intense signal at 326 mT corresponds to Zeeman transition, the $`g`$ value is estimated to be 2.06; the value larger than the free-electron $`g`$ value of 2.0023 implies that the center is a hole center. C. P. Slichter (1990) Indeed, from the comparison with Pb3+ in KCl:Pb, D. Schoemaker and J. L. Kolopus (1970) the ESR signals are ascribed to hole centers of Pb3+. The spin Hamiltonian $``$ of the hole center is given by

$$=\mu _B𝐁\underset{¯}{g}𝐒+𝐒\underset{¯}{A}𝐈\mu _n𝐁\underset{¯}{g}_N𝐈,$$
(1)
where $`\mu _B`$ denotes the Bohr magneton, $`𝐁`$ magnetic field vector, $`\underset{¯}{g}`$ the Zeeman tensor, $`𝐒`$ the electron spin, $`\underset{¯}{A}`$ the hyperfine tensor, $`\mu _n`$ the nuclear magneton of 207Pb ($`\mu _n=0.5892\mu _N`$, $`\mu _N\text{: the nuclear magneton}`$), $`𝐈`$ the nuclear spin, and $`\underset{¯}{g}_N`$ the nuclear Zeeman tensor. We note that the first-order hyperfine interaction of the hole with surrounding Cl-nuclei is not included in the Hamiltonian because our experimental results give no evidence of the superhyperfine (SHF) effect that the interaction splits each resonance at 326, 522, and 1400 mT in Fig. 2 into tens of fine resonances as observed in PbF2 (Ref. M. Nishi et al., 1977). Equation (1) describes the center that a hole strongly localizes on a Pb2+ ion, namely, self-trapping hole center of Pb3+.

Equation (1) for $`I=0`$ is reduced to the electron Zeeman term. The intense signal at 326 mT in Fig. 2 slightly depends on rotation angles. Spin Hamiltonian analysis for the Zeeman transition provides principal $`g`$ values as shown in Table 1; we set $`x=c`$, $`y=b`$, and $`z=a`$ in this analysis.

In analyzing the spin Hamiltonian for $`I=1/2`$, we can assume that the $`A`$ tensor is isotropic because the resonance at 522 mT is independent of rotation angles. Furthermore, we replace, for simplicity, the contribution of nuclear Zeeman term to the energy eigenvalues with the effective nuclear $`g_N`$ value along the corresponding magnetic field. The simplification is justified because the contribution of the nuclear Zeeman term to Eq. (1) is small enough; indeed, the resonances are described by the electron Zeeman and isotropic hyperfine terms in a good approximation. Pb3+ centers in other host crystals D. Schoemaker and J. L. Kolopus (1970); R. Röhrig and J. Schneider (1969); J. L. Kolopus et al. (1970); K. Suto and M. Aoki (1969, 1968) were analyzed within this approximation. However, to estimate $`g_N`$ values, we choose to include the effective value into the energy eigenvalues. The obtained equations of the eigenvalues are the same as Breit-Rabi formula, G. Breit and I. I. Rabi (1931) which was applied to Pb3+ centers in other hosts. D. Schoemaker and J. L. Kolopus (1970); R. Röhrig and J. Schneider (1969); J. L. Kolopus et al. (1970); K. Suto and M. Aoki (1969, 1968) Figure 9 depicts energy diagram of Eq. (1) for $`\text{B}a`$; broken lines denote energy levels for $`I=0`$, and solid lines for $`I=1/2`$. Arrows in Fig. 9 represent the ESR transitions observed in the measurement. Numerical estimation on $`g_N`$ gives the values between 0.1 and 6 for various directions of B. The anisotropy of the $`g_N`$ tensor is responsible for the rotation-angle dependence of the ESR signals around 1400 mT; moreover, the rotation-angle dependence indicates the deviation of principal $`g_N`$ axes from the $`a`$, $`b`$, and $`c`$ axes. In the unit cell of PbCl2 crystal, there exist two-equivalent Pb-ion sites which reflect the crystallographic symmetry. The twofold splits around 1400 mT in Fig. 2 are explained by the two possible configurations of Pb3+ centers in the unit cell and by the anisotropy of the $`g_N`$ tensor.

The evaluated $`g`$ and $`A`$ values are listed in Table 1 together with the $`g`$ and $`A`$ values of Pb3+ centers in other hosts. The $`g`$ values are about 2 in all hosts, while the $`A`$ values vary in 16–37 GHz. The $`A`$ values imply that the spatial spread of the hole is quite different in each host.

### IV.2 Thermal stability of ESR signals and PL bands

Below 70 K holes localize on Pb2+ ions and form self-trapping hole centers of Pb3+, and, on the other hand, electron centers are not detected at 0–1700 mT below 50 K. As STEL centers with simple configuration, monomer Pb+ and dimer Pb23+ centers are possible in PbCl2. Indeed, Pb23+ centers are observed above 60 K. Pb+ centers usually have $`g`$ value of 1.0–1.6 in Pb-doped alkali chloride; E. Goovaerts et al. (1983) in our measurement, the ESR signal would appear at 400–700 mT if it exists. However, the STEL centers of Pb+ have not been detected. Thus, it is improbable that the Pb+ centers are induced in PbCl2.

The sharp TL growth at 55 K in Fig. 5 indicates the thermal activation of trapped carriers. Because the STEL centers of Pb23+ appear at 60 K and the hole centers of Pb3+ are quite stable at 60 K as shown in Fig. 3, the activated carriers at 55 K are ascribed to electrons. However, the trapped state of electrons below 50 K has not been observed at 0–1700 mT. The electron center is most likely to has either of the following structures; (i) the center with ESR in the region higher than 1700 mT, or (ii) the center without ESR. We discuss in Sec. IV.4 the relaxation dynamics of electrons below 50 K, producing the trapped state.

The ESR spectra in Fig. 3 show that Pb3+ centers thermally change into the A center above 70 K and are finally replaced at 90 K. In a pulse-annealing experiment S. V. Nistor et al. (1998) on PbCl:Tl, the A signal is weaken under annealing at 200 K, and the ESR signals coming from hole-trapping centers of Tl2+ grow at the temperature. The result implies that the A signal originates from hole-trapping centers. The STEL centers of Pb23+ appear above 60 K as shown in Figs. 3 and 4, become unstable thermally above 130 K, and are quenched around 210 K. S. V. Nistor et al. (1993, 1998)

Figure 10 summarizes and schematically represents the thermal stability of ESR signals and PL bands; solid lines stand for the stable range, and dotted lines denote unstable but still detectable range. Blue PL in Fig. 10 denotes the blue PL band at 2.79 eV in Fig. 7, and X does the broad PL band around 2 eV in Fig. 6. Obviously, the BG-PL band is thermally coincident with the STH centers of Pb3+. In addition, the thermal activation of electrons at 55 K corresponds to the TL which has the same shape with the BG-PL band. Consequently, we ascribe the luminescent state yielding the BG-PL band to the STE associated with a Pb3+ center; probably, the STE has the configuration of (Pb3+ $`+`$ electron). The disagreement of the BG-PL band with Pb23+ centers in Fig. 10 excludes the model for the BG-PL band proposed in Refs. M. Kitaura and H. Nakagawa, 2001; M. Kitaura et al., 2000; S. V. Nistor et al., 2000; V. Babin et al., 2002.777From the experimental evidence presented already, we can also discuss the models for the UV-PL and 2.88-eV blue-PL bands in Refs. M. Kitaura and H. Nakagawa, 2001; M. Kitaura et al., 2000; S. V. Nistor et al., 2000; V. Babin et al., 2002; the absence of Pb+ centers denies the model in Refs. M. Kitaura and H. Nakagawa, 2001; M. Kitaura et al., 2000; S. V. Nistor et al., 2000, and the disagreement of the temperature range of Pb23+ centers with those of the UV-PL and blue-PL bands excludes the model in Ref. V. Babin et al., 2002. The blue PL band at 2.79 eV almost corresponds to the STEL centers of Pb23+ and the A centers. Therefore, this study provides a possibility that the blue PL band comes from the STE’s associated with Pb23+ centers, but, to identify the origin, the further study with optically detected magnetic resonance technique is surely needed.

### IV.3 Origin of “A signal”

The origin of the A signal has been disputed over the past three decades; it was once attributed to electron centers of Pb+ (Refs. W. C. De Gruijter and J. Kerssen, 1972 and J. Kerssen et al., 1973), but the properties of the A signal, the $`g`$ value and the ESR spectrum, are far different from those of Pb+ in other host crystals. P. G. Baranov and J. Rosa (1990)

The A signal was recently assigned to self-trapping hole centers of Cl2- (VK centers). S. V. Nistor et al. (1998) The A signal is composed of five resonances as presented in Fig. 1; the intensity ratio at 9 K is estimated to be $`1:10:27:10:0.5`$. However, the ESR spectrum of Cl2- splits into seven resonances in the first-order hyperfine effect, and the intensity ratio of $`1:2:3:4:3:2:1`$ disagrees with that of the A signal. Moreover, the rotation-angle dependence of the A signal W. C. De Gruijter and J. Kerssen (1972) does not show the anisotropy peculiar to the dimer-molecular VK centers, R. H. Silsbee (1972) but is almost isotropic. Thus, the A signal is unlikely to originate from the VK-type hole centers of Cl2-.

Furthermore, the A signal of five resonances does not come from the Pb3+ centers with SHF interaction as observed in PbF2 (Ref. M. Nishi et al., 1977), because (i) the satellite at 522 mT disappears up to 90 K as shown in Fig. 3 and (ii) the SHF structure, which stems from the interaction of the Pb3+ centers with the surrounding Cl- ions, is composed of tens of fine resonances. D. Schoemaker and J. L. Kolopus (1970)

As shown in Fig. 4, the A signal appears under pulse annealing at 100 K after photoirradiated at 10 K. This result indicates that the localized state responsible for the A signal is produced by thermal transfer of the localized states induced at 10 K. In addition, Fig. 3 shows that the STEL centers of Pb23+ are stable over 80–90 K where the Pb3+ signals change into the A signal. Consequently, we declare that the A signal is formed by either of the two following ways: (i) The STH centers become unstable around 80 K and the holes transfer to other trapped state associated with permanent lattice defects. (ii) Vacancies begin to move thermally around 70 K, affect the STH centers, and modify the STH centers or make the STH center unstable. In any way, the A signal is ascribed to the hole-trapping centers associated with the permanent lattice defects such as vacancies or impurities or both.

### IV.4 Relaxation dynamics of electron-hole pairs

We discuss here the relaxation of $`e`$-$`h`$ pairs in PbCl2 from the comparison with relaxation in PbBr2 (Ref. M. Iwanaga et al., 2000).

In PbBr2, the spontaneous dissociation of $`e`$-$`h`$ pairs was reported, M. Iwanaga et al. (2000) and the individual self-trapped states of both electrons and holes have been recently evidenced with ESR technique. M. Iwanaga et al. (2002)

However, the present ESR study on PbCl2 shows that the relaxed states of $`e`$-$`h`$ pairs are STH’s and trapped electrons below 50 K, STH’s and STEL’s at 60–70 K, and the A centers and STEL’s at 80–130 K (Fig. 10). The complicated results probably come from the inevitably dense vacancies in PbCl2J. F. Verwey and J. Schoonman (1967); J. Oberschmidt and D. Lazarus (1980) PbCl2 crystals are high-ionic conductors and therefore include dense anion vacancies more than 1017 cm-3. In the crystals, the anion vacancies or the vacancy-associated defects are electron traps and can be competitors to the STEL centers of Pb23+. Indeed, the thermal production of the STEL’s in Fig. 4 suggests that the competitors are efficient enough to result in the absence of STEL’s below 50 K.

According to the theoretical study by Sumi, A. Sumi (1977) the exciton–acoustic-phonon interaction determines the relaxed state of $`e`$-$`h`$ pairs and classifies the relaxed states by the strength and the sign of the coupling constants. In the theoretical study, the crystallographic field is idealized with omitting the lattice defects such as dense vacancy, so that the study is not applicable to PbCl2 straightforwardly. However, the coexistence of STEL’s and STH’s at 60–70 K shows the evidence that both electrons and holes strongly interact with acoustic phonons. Consequently, though the localized states are far more complicated in the real crystal, we believe that the $`e`$-$`h`$ relaxation similar to that in PbBr2 does also realize in PbCl2.

At the end of discussion, we compare the relaxed states of $`e`$-$`h`$ pairs in PbF2, PbCl2, and PbBr2. Though the crystallographic structure of $`\beta `$-PbF2 is cubic and those of PbCl2 and PbBr2 are orthorhombic, R. W. G. Wyckoff (1963) STH centers in $`\beta `$-PbF2 (Ref. M. Nishi et al., 1977) and PbCl2 are monomer Pb3+ centers while STH centers in PbBr2 are dimer Br2- centers. M. Iwanaga et al. (2002) The relaxed states indicate that holes in $`\beta `$-PbF2 and PbCl2 strongly interact with Pb2+ ions while holes in PbBr2 do with Br- ions. The top of the valence band in PbCl2 is composed of about half-to-half Pb2+ ($`6s`$) and Cl- ($`3p`$), M. Fujita et al. (2000) but the holes nevertheless localize only on Pb2+ ions. On the other hand, though the bottoms of the conduction band in $`\beta `$-PbF2, PbCl2, and PbBr2 are composed of the $`6p`$ states of Pb2+ ions, M. Nizam et al. (1988); M. Fujita et al. (2000) electrons in $`\beta `$-PbF2 do not get self-trapped while electrons in PbCl2 and PbBr2 form STEL centers of Pb23+. From the comparisons here, we remark that in lead halides the structure of electronic band does not simply determine the relaxed states of $`e`$-$`h`$ pairs, but the electron-phonon and the hole-phonon interaction plays a crucial role to determine the relaxed states.

## V CONCLUSIONS

We have comprehensively investigated photoinduced ESR signals and PL in a wide range of 5–200 K in PbCl2. As a result, the hole centers below 70 K have been found to be self-trapping centers of Pb3+. The ESR study in the wide temperature range reveals the thermal change of localized centers; in particular, the grow of the STEL centers of Pb23+ and the thermal transfer from the STH centers to the A centers. From the comparison with the thermal stability of the localized centers, the origins of PL bands have been discussed; we finally conclude that the STH centers of Pb3+ are responsible for the STE’s yielding the BG-PL band at 2.50 eV.

###### Acknowledgements.

We would like to thank Mr. I. Katayama and Mr. T. Hasegawa for technical assistance in ESR experiments.


text:
# Instability of isolated triplet excitations on the Shastry-Sutherland lattice (SSL)

## I Introduction

The discovery of plateaus in the magnetization curve $`M=M(B)`$ of the compound $`\mathrm{SrCu}_2(\mathrm{BO}_3)_2`$ kageyama99 ; onizuka00 ; nojiri99  at rational values of the magnetization $`M/M_S=1/3,1/4,1/8`$ ($`M_S=1/2`$) has led to intensive investigations of the ground state properties of the Shastry-Sutherland model shastry81  with Hamiltonian

$`H`$ $`=`$ $`{\displaystyle \underset{𝐱,𝐲}{}}𝐒(𝐱)𝐒(𝐲)+\alpha {\displaystyle \underset{𝐱,𝐲}{}}𝐒(𝐱)𝐒(𝐲).`$ (1)
The spin-1/2 couplings extend over nearest ($`𝐱,𝐲`$) and specific next-nearest ($`𝐱,𝐲`$) neighbor couplings, which define the SSL, shown in Fig. 1.

In the absence of an external field ($`M=0`$) the ground state can be represented by a product of singlet states on the SSL if $`\alpha `$ exceeds a critical value $`\alpha _c`$, which has been found to be $`\alpha _c=1.43`$ in Ref. miyahara99, ; weihong01, . This value is very close to the coupling $`\alpha ^{}=1.48`$, which seems to be realized in the compound $`\mathrm{SrCu}_2(\mathrm{BO}_3)_2`$. In order to describe the magnetic properties of the compound – in particular for fixed magnetizations $`M=1/4,1/6,1/8,1/12,1/16`$ where plateaus are expected or found – several ordering patterns have been proposed and discussed in the literature. kageyama99 ; onizuka00 ; nojiri99 ; miyahara99 ; momoi00 ; fukumoto00 ; miyahara00  They all have in common that in the sector with total spin $`S`$, $`N_T=S`$ triplets and $`N_S=N/2N_T`$ singlets are distributed over the SSL with $`N`$ sites. Typical examples of these singlet-triplet configurations are shown in Ref miyahara00, . In contrast to the pure singlet configuration (Fig. 1) the singlet-triplet configurations are not eigenstates of the Hamiltonian (1). Moreover, it has been shown in our previous paper fle02  that the formation of triplets on the SSL is disadvantegeous if the coupling $`\alpha `$ falls below a certain critical value $`\alpha _c(M)`$, depending on $`M`$. In particular, the singlet-triplet configurations proposed in Fig.8 of Ref. miyahara00,  cannot be considered as adequate variational states for $`M=1/8`$, since $`\alpha _c(M=1/8)=2.3>\alpha ^{}`$. As an alternative, we proposed in Ref. fle02,  (Fig.4) a “monomer-dimer configuration” built up from monomers (i.e. isolated spin-up states) and dimers (i.e. singlets) on nearest and next-nearest neighbor bonds.

It is the purpose of this Letter, to prove that the instability of isolated triplet excitations on the SSL is a quite general feature for $`\alpha <2`$ and low magnetizations $`M1/8`$.

## II Singlet-triplet versus monomer-dimer configurations

The variational states $`|K,\nu `$ which are constructed from the monomer-dimer configurations generalize the familiar singlet-triplet configurations on the SSL in the following sense: In the sector with total spin $`S`$ we have $`\nu =2S`$ monomers – i.e. isolated spin-up states $`|𝐱_j+`$ $`j=1,\mathrm{},\nu `$ at sites $`𝐱_1\mathrm{}𝐱_\nu `$. They form the ferromagnetic cluster ($`\nu `$). All remaining sites $`𝐱,𝐲,\mathrm{}`$ are occupied with $`(N\nu )/2`$ singlets (dimers) $`[𝐱,𝐲]`$. They form the antiferromagnetic cluster ($`K`$). Each monomer and dimer configuration defines a variational state:

$`|K,\nu `$ $`=`$ $`{\displaystyle \underset{j=1}{\overset{\nu }{}}}|𝐱_j+{\displaystyle \underset{𝐱,𝐲K}{}}[𝐱,𝐲].`$ (2)
The expectation value of Hamiltonian (1) between these states turns out to be fle02

$`K,\nu |H|K,\nu `$ $`=`$ $`{\displaystyle \frac{3}{4}}\left(N_1^{(0)}(K)+\alpha N_2^{(0)}(K)\right)`$ (3)
$`+{\displaystyle \frac{1}{4}}\left(N_1^{(1)}(\nu )+\alpha N_2^{(1)}(\nu )\right)`$
where $`N_1^{(0)}(K)`$ and $`N_1^{(1)}(\nu )`$ are the numbers of nearest neighbor singlets on ($`K`$) and monomer pairs on ($`\nu `$), respectively. $`N_2^{(0)}(K)`$ and $`N_2^{(1)}(\nu )`$ denote the corresponding numbers on the next-nearest neighbors according to Fig. 1. The singlet-triplet configurations on the SSL are special monomer-dimer configurations with:

$`N_1^{(0)}=0,N_2^{(0)}={\displaystyle \frac{N\nu }{2}}`$ , $`N_1^{(1)}=0,N_2^{(1)}={\displaystyle \frac{\nu }{2}},`$ (4)
i.e. we have a maximum number of dimers (singlets) and monomer pairs (triplets) on the SSL. Due to the geometry of the SSL it is not possible to maximize the number of singlets $`N_2^{(0)}`$ and to minimize the number of triplets $`N_2^{(1)}`$ at the same time. Here begins the problem with triplet excitations on the SSL: For smaller values of $`\alpha `$ \[$`\alpha <\alpha _c(M)`$\], the break up of the triplets into well separated monomer pairs is favored energetically. For $`M1/8`$ – where the triplets on the SSL are well isolated (cf. Figs. 8,9,10 in Ref. miyahara00, ) – we can study the break up of each triplet and the change of the local environment in the monomer-dimer configuration directly, as is shown in Fig. 2(a),(b). The configuration ($`K_a,\nu _a`$) in Fig. 2(a) shows a triplet at sites $`𝐱`$ and $`𝐲`$ embedded in a sea of singlets on the SSL. They are represented by the solid lines in Fig. 2(a). The triplet is broken up in a pair of monomers at sites $`𝐱`$ and $`𝐲`$ separated by a “knight’s move” \[cf. Fig. 2(b)\]. Comparing the energies of the configurations ($`K_a,\nu _a`$) and ($`K_b,\nu _b`$) we have to decrease $`N_2^{(0)}`$ and $`N_2^{(1)}`$ and to increase $`N_1^{(0)}`$ by one unit:

$`\mathrm{\Delta }E`$ $`=`$ $`K_b,\nu _b|H|K_b,\nu _bK_a,\nu _a|H|K_a,\nu _a`$ (5)
$`=`$ $`{\displaystyle \frac{1}{2}}\left(\alpha {\displaystyle \frac{3}{2}}\right).`$
The energy difference (5) is negative for $`\alpha <3/2`$. Therefore, the break up of the triplet is favored in this regime. We will see in the next section, that this phenomenon occurs already at larger values of $`\alpha `$, if we improve our variational ansatz.

## III Magnetic order and the frozen monomer approximation

The monomer-dimer configurations are not eigenstates of the Hamiltonian (1). However, it might happen that the ground state is governed by a specific distribution ($`\nu `$) of “frozen” monomers. They define the magnetic ordering of the ground state. The variational ansatz (2) will be improved if we substitute the product of dimers

$`{\displaystyle \underset{𝐱,𝐲K}{}}[𝐱,𝐲]`$ $``$ $`\mathrm{\Psi }(K)`$ (6)
by the ground state $`\mathrm{\Psi }(K)`$ of the antiferromagnetic cluster Hamiltonian $`H(K)`$:

$`H(K)\mathrm{\Psi }(K)`$ $`=`$ $`E(K)\mathrm{\Psi }(K).`$ (7)
$`H(K)`$ contains all nearest and next-nearest neighbor couplings on the antiferromagnetic cluster $`K`$. In Fig. 2(a),(b) they are represented by the solid singlet lines and the dotted lines connecting them.

The variational ansatz (6) yields an upper bound on the ground state energy $`E_0(M=\nu /2N)E(K,\nu )`$ in the sector with magnetization $`M`$, where

$`E(K,\nu )`$ $`=`$ $`{\displaystyle \frac{1}{4}}\left(N_1^{(1)}(\nu )+\alpha N_2^{(1)}(\nu )\right)+E(K).`$ (8)
Concerning the triplet-singlet configuration in Fig. 2(a), the ground state $`\mathrm{\Psi }(K_a)`$ of the antiferromagnetic cluster Hamiltonian $`H(K_a)`$ is again given by the product of singlets on the SSL. Note that each singlet (e.g. $`[1,2]`$) is accompanied by two nearest neighbor couplings $`𝐒(1)𝐒(z)`$, $`𝐒(2)𝐒(z)`$ such that the total spin operator $`𝐒(1)+𝐒(2)`$ acts on the singlet $`[1,2]`$. For this reason the ground state energy cannot be lowered in the case ($`K_a,\nu _a`$).

The situation is different in configurations with isolated monomers. The ground state $`\mathrm{\Psi }(K_b)`$ of the antiferromagnetic cluster is not identical with the dimer product shown in Fig.\[2(b)\]. If we apply here the couplings $`𝐒(2)𝐒(3)`$, $`𝐒(4)𝐒(5)`$ and $`𝐒(4)𝐒(7)`$ onto the nearest neighbor singlet $`[3,4]`$ a new state is created. Therefore, the ground state energy $`E(K_b)`$ of the antiferromagnetic cluster $`K_b`$ will be lower than the expectation value of the corresponding monomer-dimer configuration in Fig. 2(b). This will shift the critical value $`\alpha _c`$ where the triplet excitation becomes unstable to larger values $`\alpha _c>3/2`$. Indeed, we can derive an improved lower bound for $`\alpha _c`$, if we substitute the dimers $`[1,2][3,4][5,6][7,8]`$ by an antiferromagnetic cluster with 8 sites $`1,\mathrm{},8`$ as shown in Fig. 2(c). The ground state energy $`E_8(\alpha )`$ of the 8-site cluster is lower than the energy of the corresponding dimer configuration in Fig. 2(b) by an amount

$`\mathrm{\Delta }_8(\alpha )`$ $`=`$ $`{\displaystyle \frac{3}{4}}(3\alpha +1)E_8(\alpha );`$ (9)
$`\mathrm{\Delta }_8(\alpha )`$ is shown in Fig. 3. The straight line $`\mathrm{\Delta }E=(\alpha 3/2)/2`$ represents the energy difference (5). Therefore, the intersection point

$`\alpha _c`$ $`=`$ $`1.95`$ (10)
yields the critical value, where the instability of the triplet sets in. Enlarging the antiferromagnetic surrounding of the frozen monomer pair in Fig. 2(c) leads to an increase of the critical value (10). However, the effect is small: a calculation with a 16-site cluster – containing the 8-site cluster – yields $`\alpha _c=1.97`$.

The changes in the magnetic order from an isolated triplet on the SSL to a pair of monomers separated by a “knight’s move” can be tested by measuring the spin-spin structure factors, which are obtained from spin-spin correlators $`S_3(𝐱)S_3(𝐲)`$.

The expectation values of the spin-spin correlators can be read off from the monomer-dimer configurations:

$`K\nu |S_3(𝐱)S_3(𝐲)|K\nu `$ $`=`$ $`{\displaystyle \frac{1}{4}}\left\{\delta ^{(1)}(𝐱,𝐲)\delta ^{(0)}(𝐱,𝐲)\right\}`$
where $`\delta ^{(1)}(𝐱,𝐲)=1`$ and $`\delta ^{(0)}(𝐱,𝐲)=1`$ only if $`(𝐱,𝐲)`$ coincides with nearest or next-nearest neighbor bonds on $`(K,\nu )`$ occupied with a monomer pair or a dimer, respectively. In all other cases $`\delta ^{(j)}(𝐱,𝐲)=0`$. Note in particular, that all correlators with one site $`𝐱`$ on the ferromagnetic cluster $`\nu `$ and the other site $`𝐲`$ on the antiferromagnetic cluster $`K`$ vanish.

In the frozen monomer approximation with an antiferromagnetic cluster wavefunction $`\mathrm{\Psi }(K)`$, (III) can be extended to

$`\mathrm{\Psi }(K),\nu |S_3(𝐱)S_3(𝐲)|\mathrm{\Psi }(K),\nu `$ $`=`$ (12)
$`{\displaystyle \frac{1}{4}}\delta ^{(1)}(𝐱,𝐲)+\mathrm{\Psi }(K)|S_3(𝐱)S_3(𝐲)|\mathrm{\Psi }(K)\delta \left(𝐱,𝐲K\right).`$
Note that (III) and (12) differ in the correlations $`S_3(𝐱)S_3(𝐲)`$, $`𝐱,𝐲K`$ on the antiferromagnetic cluster $`K`$.

## IV Coexistence of stable and unstable triplet excitations on the SSL for $`M=1/6`$

The instability discussed so far only concerns “isolated” triplets on the SSL. The density of triplets $`N_T/N=M`$ is controlled by the magnetization $`M`$ and raises the question, what happens in the cases $`M=1/4`$ and $`M=1/6`$. A typical singlet-triplet configuration for $`M=1/4`$ on the SSL is given in Fig. 6(a) of Ref. miyahara00, . Breaking up a triplet in these configurations produces additional monomer pairs, which increases the energy, i.e. a high density of triplets prevents their instability. In the case $`M=1/6`$, the triplets on the SSL form stripes as is shown in Fig. 4(a). Interesting enough, each second stripe of the triplets can break up as is demonstrated in Fig. 4(b). Comparing the energies of the configurations $`(K_a,\nu _a)`$ and $`(K_b,\nu _b)`$, we find again, that the energy difference (5) per triplet changes sign for $`\alpha _c(M=1/6)=3/2`$.

Note, that the isolated monomers along one stripe in Fig. 4(b) are accompanied with a quasi-onedimensional antiferromagnetic cluster $`K`$. We have computed the ground state energy of the 24 site clusters $`E_{24}(\alpha ,M=1/4)`$, which surrounds the 4 pairs of monomers arising from the break up of 4 triplets on the SSL, shown in Fig. 4(b). The energy difference (per triplet)

$`\mathrm{\Delta }_{24}(\alpha ,1/6)`$ $`=`$ $`{\displaystyle \frac{1}{4}}\left\{{\displaystyle \frac{3}{4}}(8\alpha +4)E_{24}(\alpha ,1/6)\right\}`$ (13)
is plotted in Fig. 3. It meets the straight line $`(\alpha 3/2)/2`$ at

$`\alpha _c(M=1/6)`$ $`=`$ $`1.985.`$ (14)
This improved lower bound for $`\alpha _c(M=1/6)`$ differs from the lower bound we found in Ref. fle02, . There we did not realize, that a mixture of triplets on the SSL and isolated monomers – as shown in Fig. 4(b) – lowers the energy more efficiently.

## V Discussion and conclusions

In this Letter, we have investigated the stability of triplet excitations on the Shastry-Sutherland lattice. Our results can be summarized as follows:

(i) Isolated triplets turned out to be unstable if the ratio of next-nearest to nearest neighbor couplings is smaller than $`\alpha <\alpha _c2.0`$. This implies that the magnetic properties of $`\mathrm{SrCu}_2(\mathrm{BO}_3)_2`$ – where the coupling ratio is $`\alpha ^{}1.48`$ – cannot be understood in terms of isolated triplet excitations on the SSL, if the magnetization $`M`$ is small enough ($`M1/8`$). This statement holds in particular for the triplet ordering patterns for $`M=1/8,1/12,1/16`$ in Figs. 8,9,10 of Ref. miyahara00, .

(ii) For $`M=1/6`$ \[Fig. 7(a) in Ref. miyahara00, \] the triplets form stripes on the SSL. It turns out that the triplets on each second stripe break up into isolated monomers if $`\alpha \alpha _c(M=1/6)=1.985`$.

(iii) The triplets on the SSL in the configuration for $`M=1/4`$ \[Fig.6(a) in Ref. miyahara00, \] appears to be stable for $`\alpha =\alpha ^{}`$. This demonstrates, that triplet excitations on the SSL are stabilized if the triplet density is high enough.

Breaking up the isolated triplet into two monomers (spin-up states) at sites x and y separated by a “knight’s move” \[Fig. 2(c)\] lowers the energy of the new configuration in two ways:

1. There is a “classical” effect, which results from the rearrangement of singlets and triplets on $`(K_a,\nu _a)`$ \[in Fig. 2(a)\] into the monomer-dimer configuration $`(K_b\nu _b)`$ \[in Fig. 2(b)\].
2. There is a “quantum” effect produced by the antiferromagnetic cluster, which surrounds the monomers at sites x and y \[Fig. 2(c)\].

###### Acknowledgements.

We are indebted to M. Karbach for a critical reading of the manuscript.


text:
# Vortex fluctuations in underdoped Bi2Sr2CaCu2O8+δ crystals

## Abstract

Vortex thermal fluctuations in heavily underdoped Bi2Sr2CaCu2O8+δ ($`T_c`$=69.4 K) are studied using Josephson plasma resonance (JPR). From the zero-field data, we obtain the $`c`$-axis penetration depth $`\lambda _{L,c}(0)=230\pm 10`$ $`\mu `$m and the anisotropy ratio $`\gamma (T)`$. The low plasma frequency allows us to study phase correlations over the whole vortex solid state, and to extract a wandering length $`r_w`$ of vortex pancakes. The temperature dependence of $`r_w`$ as well as its increase with dc magnetic field is explained by the renormalization of the vortex line tension by the fluctuations, suggesting that this softening is responsible for the dissociation of the vortices at the first order transition.

Vortex thermal fluctuations are considered essential in determining the $`(H,T)`$ phase diagram of layered high temperature superconductors (HTS), and notably the first order transition (FOT) in which the ordered vortex crystal transforms to a liquid state without long range phase coherence Cubitt93 ; Zeldov95 . Many scenarios, varying from vortex lattice melting described by a Lindemann criterion Blatter96  to layer decoupling Koshelev91 ; Daemen93 ; Dodgson00 , all considering various degrees of coupling between the superconducting layers, have successfully been used to describe the position of the FOT in the $`(H,T)`$–plane. However, such fits to the FOT line have not been able to convincingly discriminate between the different models. Here, we aim to do just this, through a direct measurement of the amplitude, as well as the field and temperature dependence of vortex thermal excursions in the vortex solid phase (or “Bragg–glass” Giamarchi97 ) that lead to the FOT.

For this study, we use the layered Bi2Sr2CaCu2O8+δ (BSCCO) compound, in which vortex excursions can conveniently be measured by the Josephson Plasma Resonance (JPR) technique Tsui94 ; Gaifullin00 ; Shibauchi99 . Briefly, the interlayer Josephson current $`J_m^{(c)}`$ can be measured through the JPR frequency $`\omega _{pl}J_m^{(c)1/2}`$, at which the equality of charging and kinetic energy leads to a collective excitation of Cooper pairs across the layers. In turn, $`\omega _{pl}^2(B,T)=\omega _{pl}^2(0,T)\mathrm{cos}(\varphi _{n,n+1})`$ intimately depends on the gauge-invariant phase difference $`\varphi _{n,n+1}`$ between adjacent layers $`n`$ and $`n+1`$ Bulaevskii95 . Here, $`\mathrm{}`$ stands for thermal and disorder averaging. Thus, JPR is a probe of the interlayer phase coherence. The fluctuations of vortex lines created by a dc magnetic field applied perpendicularly to the layers modify the relative phase difference between adjacent layers and thus depress $`\omega _{pl}`$. In Bi2Sr2CaCu2O8+δ, the ensemble of vortex lines should be described as stacks of two-dimensional pancake vortices. Thermal fluctuations shift the individual vortex pancakes with respect to their nearest neighbors in the $`c`$ direction, by a distance $`𝐫_{n,n+1}=𝐮_{n+1}𝐮_n`$. Here un is the $`ab`$-plane displacement of the pancake vortex in layer $`n`$ with respect to the equilibrium position of the stack it belongs to (Fig. 1). The wandering length of vortex lines, which is related directly to the JPR frequency $`\omega _{pl}^2`$, can be then defined as $`r_w=𝐫_{n,n+1}^2^{1/2}`$ Bulaevskii00 ; Koshelev00 . Below, we shall only consider temperatures above $`T=42`$ K, at which vortex pinning (quenched disorder) is unimportant Zeldov95 ; Avraham01 .

Underdoped BSCCO ($`T_c`$ = 69.4 K) single crystals were grown by the traveling solvent floating zone method in 25 mbar O2 partial pressure at the FOM-ALMOS center, the Netherlands MingLi02 . The samples were post-annealed for one week at 700C in flowing N2. The advantage of using heavily underdoped BSCCO is that $`\omega _{pl}(0,0)`$ 61 GHz turns out to be very low, which allows us to measure the vortex meandering over the entire vortex phase diagram. Samples A and B (cut from the same crystal) have dimensions $`1.35\times 1\times 0.04`$ mm3 and $`0.7\times 0.47\times `$$`0.04`$ mm3, respectively. Another sample from the same batch was used to determine the temperature of the FOT (Fig. 5b, inset), by measuring the paramagnetic peak at the FOT with a miniature Hall probe magnetometer Morozov96 .

The JPR measurements were carried out using the cavity perturbation technique in the Laboratoire des Solides Irradiés (on sample A) and the bolometric method in the Institute for Solid State Physics at the University of Tokyo (on samples A and B). For the cavity perturbation technique, the sample was glued in the center of the top cover of a cylindrical Cu cavity used in the different TM01i ($`i=0,\mathrm{},4`$) modes. These provide the correct configuration of the microwave field at the sample location, in which $`E_{rf}c`$-axis and $`H_{rf}0`$ Colson02 . The unloaded quality factor $`Q_0`$ is measured as function of temperature and field to obtain the power absorbed by the sample (Fig. 2). The bolometric method Matsuda94  consists in measuring the heating of the sample induced by the absorption of the incident microwave power when the JPR is excited Gaifullin00 ; Colson02 . Furthermore, reversible magnetization measurements were carried out on sample A using a commercial superconducting quantum interference device magnetometer in order to extract the London penetration depth $`\lambda _{L,ab}(T)`$ for currents in the $`ab`$–plane MingLi02 .

Figure 3 shows the JPR frequency $`f_{JPR}=\omega _{pl}/2\pi `$ in zero field obtained by the above-mentioned methods on samples A and B. $`\omega _{pl}^2`$ is proportional to the maximum interlayer Josephson current along the $`c`$-axis Bulaevskii95 ,

$$\omega _{pl}^2(H,T)=\omega _{pl}^2(0,T)\mathrm{cos}(\varphi _{n,n+1})=\frac{2\pi \mu _0c^2s}{ϵ_r\mathrm{\Phi }_0}J_m^{(c)}(B,T)$$
(1)
where $`J_m^{(c)}(B,T)=J_m^{(c)}(0,T)\mathrm{cos}(\varphi _{n,n+1})`$ is the maximum Josephson current, $`s=1.5`$ nm is the interlayer spacing, $`ϵ_r`$ the high-frequency relative dielectric constant and $`\mathrm{\Phi }_0`$ the flux quantum. Using $`\omega _{pl}(0,T)=c/\lambda _{L,c}(T)\sqrt{ϵ}_r`$ and $`ϵ_r`$=11.5 Gaifullin01 , we obtain the London penetration depth for currents along the $`c`$-axis, $`\lambda _{L,c}(T)`$. When divided by the $`\lambda _{L,ab}(T)`$–data from reversible magnetization, this yields, without any model assumptions, the anisotropy parameter $`\gamma (T)\lambda _{L,c}(T)/\lambda _{L,ab}(T)`$, shown in the Inset to Fig. 3. Typically, at $`T=0.5T_c`$, $`\lambda _{L,c}240\mu `$m and $`\lambda _{L,ab}400`$ nm, so that $`\gamma 600`$, consistent with other data for the same material Gaifullin00 . Note that $`\gamma `$ decreases as function of temperature.

To analyze our JPR data in non-zero magnetic fields, we should divide $`\omega _{pl}(B,T)`$ by the zero–field result depicted in Fig. 3. In the absence of a model that satisfactorily describes $`\omega _{pl}(0,T)`$ over the whole temperature range, we resort to a spline fit to the experimental data. Next, we extract the vortex wandering length $`r_w`$ as follows. In the single vortex regime, at very low fields $`B<B_J=\mathrm{\Phi }_0/\lambda _J^2`$, $`B<B_\lambda =\mathrm{\Phi }_0/4\pi \lambda _{L,ab}^2`$, Bulaevskii and Koshelev derived Bulaevskii00 ; Koshelev00

$$1\frac{\omega _{pl}^2(B,T)}{\omega _{pl}^2(0,T)}\frac{\pi B}{2\mathrm{\Phi }_0}r_w^2\mathrm{ln}\frac{\lambda _J}{r_w}$$
(2)
where the Josephson length $`\lambda _J=\gamma s`$. We stress that this relation is meaningful only for small excursions $`r_w0.6\lambda _J`$, i.e. for $`\mathrm{cos}(\varphi _{n,n+1})=\omega _{pl}^2(B,T)/\omega _{pl}^2(0,T)1`$. More generally, one expects an increase of $`1\mathrm{cos}(\varphi _{n,n+1})`$ with $`r_w`$ up to a plateau for large $`r_w`$, as was found in recent simulations of the evolution of $`1\mathrm{cos}(\varphi _{n,n+1})`$ versus $`u/a_0r_w/a_0`$ for a pancake gas ($`a_0=\sqrt{\mathrm{\Phi }_0/B}`$ is the intervortex spacing) Brandt02 . The numerical data show that $`1\mathrm{cos}(\varphi _{n,n+1})`$ is almost quadratic in $`r_w`$ for $`01\mathrm{cos}(\varphi _{n,n+1})0.70.8`$, in agreement with Eq. (2), if the weak logarithmic dependence on $`\lambda _J/r_w`$ is disregarded. Thus, we use

$$r_w^2=\frac{2\mathrm{\Phi }_0}{\pi B}(1\mathrm{cos}(\varphi _{n,n+1}))$$
(3)
to obtain an approximation of the wandering length. Since $`r_w=(𝐮_{n+1}𝐮_n)^2^{1/2}=[2(u^2𝐮_n𝐮_{n+1})]^{1/2}`$, one has, in the case of completely uncorrelated layers (e.g. for a pancake gas), $`r_w=2𝐮_n^2^{1/2}\sqrt{2}u`$. Disregarding the “anticorrelated” situation with $`𝐮_n𝐮_{n+1}<0`$, correlations between pancake positions in different layers yield $`r_w<\sqrt{2}u`$, i.e., $`r_w`$ is a lower limit for the root mean squared (RMS) displacement $`u`$ of the vortex line.

Figure 4 shows $`1\omega _{pl}^2(B,T)/\omega _{pl}^2(0,T)=1\mathrm{cos}(\varphi _{n,n+1})`$ as function of temperature in different dc fields. The temperature dependence of the wandering length $`r_w`$, obtained by applying Eq. (3), is represented in Fig. 5. For every field, we observe an increase of $`r_w`$ with $`T`$. At constant temperature, $`r_w`$ increases with magnetic field, indicating a $`\omega _{pl}(B)`$–dependence that deviates from the expected linear behavior of Eq. (2). Another interesting feature of the $`r_w`$($`T`$) curve is the break in the slope which appears at a field-dependent temperature close to the FOT and above which all the $`r_w`$ curves merge into one. Alternatively, one may plot the same values of $`r_w`$ vs $`T/T_{FOT}`$, where $`T_{FOT}`$ is the FOT temperature (Fig. 5b). Here, two regimes appear clearly, showing the correlation of the results with the FOT. For $`T<0.96T_{FOT}`$, $`r_w(T/T_{FOT})`$ roughly overlaps for all fields, whereas for $`T>0.96T_{FOT}`$ the curves deviate from each other.

We now discuss the temperature and field dependence of $`r_w`$ in the vortex solid. The RMS thermal vortex displacement $`u`$ can be obtained by equipartition of the associated elastic energy with the thermal energy, $`U_{el}=c_{44}a_0^2(u^2/s)=k_BT`$. The vortex lattice tilt modulus

$`c_{44}(𝐤)`$ $``$ $`{\displaystyle \frac{B^2/\mu _0}{1+\lambda _c^2k_{}^2+\lambda _{ab}^2Q_z^2}}+{\displaystyle \frac{\epsilon _0}{2\gamma ^2a_0^2}}\mathrm{ln}\left[{\displaystyle \frac{k_{max}^2}{K_0^2+(Q_z/\gamma )^2}}\right]`$ (4)
$`+{\displaystyle \frac{\epsilon _0}{2\lambda _{ab}^2Q_z^2a_0^2}}\mathrm{ln}\left(1+{\displaystyle \frac{a_0^2}{21.3r_w^2}}\right),`$
calculated by Koshelev and Vinokur Koshelev98  and Goldin and Horowitz Goldin98 , consists of three terms: the nonlocal collective (lattice) term, the vortex line tension term, determined by Josephson coupling between layers, and a third term due to the electromagnetic dipole interaction between pancakes. Of particular interest here is the logarithmic correction to the temperature dependence of the second term, introduced by the cutoff $`k_{max}=\pi /r_w`$, which corresponds to the smallest meaningful deformation Koshelev98 ; Goldin98 . To proceed, we evaluate $`U_{el}`$ at the typical vortex line deformation wavevectors parallel and perpendicular to the layers, $`k_{}\pi /r_w`$ and $`Q_z\pi \gamma /2a_02\pi /s`$. Writing $`K_0=\sqrt{4\pi }/a_0`$, $`r_w^2=\alpha u^2`$ and $`x=a_0/r_w`$, equipartition yields

$`r_w^2`$ $``$ $`\alpha s^2{\displaystyle \frac{k_BT\gamma ^2}{\epsilon _0s}}[{\displaystyle \frac{4}{\pi \left(x^2+\frac{1}{4}\right)}}+{\displaystyle \frac{1}{2}}\mathrm{ln}\left(0.66x^2\right)`$ (5)
$`+{\displaystyle \frac{2}{\pi ^2}}\left({\displaystyle \frac{a_0}{\lambda _{L,ab}}}\right)^2\mathrm{ln}(1+{\displaystyle \frac{x^2}{21.3}})]^1.`$
All parameters in Eq. (5), and notably $`\epsilon _0(T)/\gamma ^2(T)=\mathrm{\Phi }_0^2/4\pi \mu _0\lambda _{L,c}^2`$, are known from experiment, which allows a direct comparison to the $`r_w(T)`$–data. Very good agreement is obtained for the magnitude, the temperature, as well as the field dependence of $`r_w`$ for the lowest three fields, using the single free parameter $`\alpha =0.95`$. For higher fields, Eq. (5) gives the correct magnitude of $`r_w`$, but too weak a temperature dependence. However, excellent fits of both the temperature and field dependence can be obtained for all fields, with the same $`\alpha =0.95`$, by omitting the nonlocal collective term, \[i.e. $`4/\pi \left(x^2+\frac{1}{4}\right)`$ in Eq. (5)\], see Fig. 5a. While the main temperature dependence of $`r_w`$ comes from the prefactor $`\gamma ^2T/\epsilon _0`$ in Eq. (5) (dotted line in Fig. 5), the behavior of $`r_w`$ in the vortex solid can only be understood as the result of the logarithmic correction arising from the softening of the line tension term by thermal fluctuations Goldin98 ; Koshelev98 . The field dependence, originating from $`Q_z`$, explicitly indicates that vortex lines are correlated (line-like) on distances that well exceed the layer spacing $`s`$.

The experimental data can also be used to compare the terms entering Eq. (4). Deep inside the vortex solid, the line tension always dominates over the magnetic coupling and the nonlocal collective contribution. At very low fields ($`B<10`$ G), the line tension term is largest all the way to the FOT. Eq. (5) then reduces to Eq. (40) of Ref. Goldin98,  with $`Q_z\pi \gamma /2a_0`$ instead of $`2\pi /s`$. At higher fields, the nonlocal collective contribution is expected to increase, eventually exceeding the Josephson coupling (line tension) term close to the FOT (for $`B>20`$ G). Nevertheless, the very good fits obtained when only the line tension term is taken into account in Eq. (5) suggest that the line tension term always dominates $`c_{44}`$ near the FOT. Moreover, we find that the electromagnetic coupling as well as the shear contribution to $`U_{el}`$ are, under all circumstances, negligible. This renders Lindemann-like Blatter96  or dislocation-mediated (Kosterlitz-Thouless like) melting, as well as the vortex–line evaporation Dodgson00  scenarios very unlikely. Rather, the large thermal excursions of pancake vortices bring about the softening of the line tension contribution to $`c_{44}`$ for the large-wavevector modes that lead to the FOT. This would comply with recent measurements showing that vortex lattice order is not a prerequisite for the FOT porous . For deformations with smaller wavevectors, Josephson coupling still contributes to the line tension even in the vortex liquid, leading to, e.g., the anisotropic vortex response to columnar defects in heavy-ion irradiated samples.

Summarizing, we have carried out JPR measurements on heavily underdoped Bi2Sr2CaCu2O8 crystals. These data yield the $`c`$–axis penetration depth, the anisotropy parameter $`\gamma (T)`$, and the wandering length of vortex lines $`r_w`$. The observed temperature and field dependences of $`r_w`$ suggest that thermal fluctuations soften the Josephson coupling contribution to the tilt modulus for short wavelengths Goldin98 , which leads us to believe that this softening drives the FOT.

We thank the Europe Scientific Foundation VORTEX program and the Nederlandse Organisatie voor Wetenschappelijk Onderzoek for financial support. PG acknowledges support of the Polish Government, grant PBZ-KBN-013/T08/19.