Characterization of Semiconductor Heterostructures and Nanostructures

1

Introduction

The Interdisciplinary Nature of and Nanotechnology and Its Need to Exploit Frontier Characterization Techniques

Giovanni Agostini and Carlo Lamberti, Department of Chemistry, NIS Centre of Excellence, and INSTM Reference Center University of Turin, Via P. Giuria 7, I-10125 Torino, Italy.

Contents

1. The Scientific and Editorial Booming of Nanotechnology in the New Millennium

2. Heterostructures and Nanostructures: Definition and Applications, from Optoelectronic to Catalysis

3. Dynamic Interplay among Growth/Synthesis Techniques, Theoretical Modeling and Characterization Techniques in the Design and Improvement of Semiconductor Heterostructure-Based Devices

4. Purposes of the Book and Chapters Layout

References

1 The Scientific and Editorial Booming of Nanotechnology in the New Millennium

The term nanotechnology refers to a branch of applied science and of technology whose unifying theme is the control of matter on the atomic and molecular scale, typically from 1 to 100 nm (1 nm = 10−9 m), and the fabrication of devices within that size range. The appeal in such approach lies in the fact that the structural, physical, chemical, electronic, optical, etc. properties of nanometer-dimensioned materials markedly differ from those of the corresponding bulk (unconfined) materials. More interestingly, such properties can be tuned acting on the material size and shape, in the 1–100 nm range. Nanotechnology, among the most advanced frontiers of Science, is certain that showing the higher degree of multidisciplinary, generated from the well-accorded interplay among different fields such as materials science, applied physics, interface and colloid science, device physics, supramolecular chemistry, physical chemistry, biochemistry, biophysics, surface science, engineering, etc. (see Table 1.1). Nanotechnology results from a combined extension of such sciences into the nanoscale.

Table 1.1

Upper part: list of Subject Categories, where the 27 journals that joined in 2005 the Subject Category named Nanoscience & Nanotechnology, were sorted in 2004 by ISI web of knowledge. As some journals belong to more than one Subject Categories, the sum of the numbers reported in the second column is larger than 27. Lower part: same data reported in the upper parts, where the Subject Categories are grouped into five macro-categories

Scientists, politicians, media and industries have much expectation concerning what new science, technology and application may result from these lines of research. Such expectations have strongly stimulated the effort made in the past years by university and industrial laboratories in the field of nanoscience and nanotechnology. A simple way to evaluate such effort is to look at the number of papers published per year that are found using nanochemistry OR nanophysics OR nanotechnology OR nanoscience as search key (Fig. 1.1a) and at the number of citations that such papers have received (Fig. 1.1b). It is evident that such simple and superficial statistical study is by far not comprehensive, as most of the papers that actually reports results in this field do not necessarily use one of those four keywords. Indeed, vide infra the last line of Table 1.3, the 66 journals belonging to the Subject Category¹ named Nanoscience & Nanotechnology have published 23,983 papers in 2011, while only 2149 have been found using those four keywords (Fig. 1.1a). So, the data reported in Fig. 1.1 are not important as absolute values that are underestimated by a factor of about 10, but for the trend they are showing. It is evident that this trend shows an impressive acceleration starting from the new millennium.

Figure 1.1 Part (a): number of papers published per year found using nanochemistry OR nanophysics OR nanotechnology OR nanoscience as search key. Spanned period 1990–September 2012; total number of papers >15,000 source ISI web of science. Part (b): number of citations received per year by the papers reviewed in part (a); total number of citations larger than 300,000. The statistic concerning year 2012, although incomplete (it refers to the first 8 months only), verifies the general trend.

Table 1.2

List of a selection of scientific journals belonging to the Subject Category named Nanoscience & Nanotechnology sorted by publishing age. The first 14 rows report selections of journals that publish only papers related to nanoscience; the last four report selection of journals, where nanoscience articles are only a fraction of the published papers. Data reported in the last two columns allow to locating each single journal belonging to the category in a pondered ranking scale

∗The journal impact factor of year Y is the average number of times articles from the journal published in (Y − 1) and (Y − 2) have been cited in year Y. Journals impact factors of year Y are usually divulgated by the Journal of Citation Reports in spring (Y + 1).

†The journal immediacy index of year Y is the average number of times an article published in year Y is cited in Y. The journal immediacy index indicates how quickly articles in a journal are cited.

Table 1.3

Evolution of the main bibliometric parameters of the Subject Category named Nanoscience & Nanotechnology from the founding year 2005–2011

∗The aggregate impact factor of year Y of a subject category is calculated the same way as the impact factor for a journal, but it takes into account the number of citations to all journals in the category in year Y and the number of articles from all journals in the category in year (Y − 1) and (Y − 2).

†The median impact factor of a subject category of year Y is the median value of all journal Impact Factors of year Y belonging to the subject category.

‡The aggregate immediacy index of year Y of a subject category is calculated the same way as the immediacy index for a journal, but it takes into account the number of citations to all journals in the category in year Y and the number of articles from all journals in the category in year Y. It indicates how quickly articles in a subject category are cited.

This scientific and technological phenomenon has been so significant that the most important publishing companies have decided to create new journals specifically devoted to this topic (see Table 1.2 for a selection of them). To the best of our knowledge, the Institute of Physics (IoP) has been the first publisher in this field, founding in the early 1990s the journal Nanotechnology (2011 impact factor 3.979), that has published so far more than 10,000 papers. This number makes Nanotechnology one of the most important journals in the field in terms of published papers. In 1999, Kluwer Academic Publishers founded the journal, Journal of Nanoparticle Research. Then, in 2001, appeared Nano Letters, from the American Chemical Society (ACS), that represents today one of the most prestigious journal in the field, with more than 7000 published papers and an impressive impact factor that, starting from 5.033 in 2002, progressively raised up to more than 13 in 2011. Among the ACS journals, excluding the review journals (Chem. Rev. and Accounts Chem. Res.), Nano Letters has become the highest impact factor journal, even exceeding the prestigious J. Am. Chem. Soc., first published in 1879. In the same year, 2001, the Elsevier journal Physica E turned its name into Physica E-low-dimensional systems & nanostructures, while the Royal Society of Chemical (RSC) launched the title Lab on a Chip (2011 impact factor 5.670) and also J. Nanosci. Nanotechnol. appeared. An important impact factor (6.024) has been achieved by the title Small, published by Wiley-VCH since 2005 (see Table 1.2). In 2006, Elsevier launched the title Nano Today, while the prestigious Nature Publishing Group entered the business with the journal Nature Nanotechnology (2011 impact factor as high as 27.270). The success of Nano Letters encouraged ACS to introduce a second title in the field devoted to full papers: ACS Nano, whose first articles appeared at the end of 2007 and that reached in 2011 an impact factor higher than 10 (forth ACS journal ranked by impact factor). In the same year, ACS decided to split the journal J. Phys. Chem. A/B into a third journal (J. Phys. Chem. C) having a significant fraction of subjects related to nanoscience. J. Phys. Chem. C rapidly becomes the highly ranked among the three: the 2011 impact factors are 2.946, 3.696 and 4.805 for A, B and C sections, respectively. Finally, when ACS decided in 2010 to add to its portfolio of physical chemistry journals an only letter journal (J. Phys. Chem. Lett.), they decided that Nanoscience & Nanotechnology should be one of the pertinent Subject Categories of this new journal, that was firstly ranked in 2011 with an impact factor of 6.213.

The progressive appearance of new journals in this field, as described above, induced the ISI web of Science (http://scientific.thomson.com/products/wos/) to introduce, in 2005, the new Subject Category¹ named Nanoscience & Nanotechnology. Twenty-seven journals joined that subject category that year. These 27 journals came mainly from the macro-area of Physics, Materials Science, Chemistry, Engineering and Biology with a percentage of 28%, 24%, 22%, 20% and 6%, respectively (Table 1.1). Again, the multidisciplinary nature of the category emerges from this statistics. The number of journals belonging to the category progressively increased year by year, reaching a value of 66 in 2011 (Table 1.3). Among them, we count journals that already had a long story, like J. Vac. Sci. Technol. B (impact factor 1.597) born in 1983, or Scripta Materialia (impact factor 2.161), or Mater. Sci. Eng. A (impact factor 1.490), or Microporous Mesoporous Mater. (impact factor 2.796), and devoted to zeolites and zeotypes that are crystalline porous materials with regular empty cavities and cages in the nanometer and subnanometer regime. The Wiley-VCH journals, Adv. Funct. Mater. and Adv. Funct. Mater., founded in 1989 and 1992, respectively, reached the Nanoscience & Nanotechnology category in 2009.

The American Institute of Physics (AIP) and the American Physical Society (APS) decided a different strategy. Starting from 2000, they selected the most pertinent papers published on the regular AIP and APS journals (Phys. Rev. Lett., Phys. Rev. A, Phys Rev. B, Appl. Phys. Lett, J. Appl. Phys., etc.) in a web collection named Virtual Journal of Nanoscale Science & Technology (http://www.vjnano.org/). Currently almost 100 journals (see http://www.virtualjournals.org/vjs/partpub.jsp for a complete list), including Science and Nature, Nature-satellite, IoP, RSC, SPIE (International Society for Optics and Photonics, formerly Society of Photographic Instrumentation Engineers), AVS (Science and Technology of Materials, Interfaces, and Processing, formerly American Vacuum Society), ASA (Acoustical Society of America), etc., joined this virtual journal.

The Subject Category Nanoscience & Nanotechnology progressively improved all bibliometric factors in a significant way in the 7 years covering the founding (in 2005) till the last data referred to year 2011 and published by the Journal of Citation reports in spring 2012. In particular, improvements concern: (1) number of journals belonging to the Subject Category (+144%); (2) number of published papers (+228%); (3) citations obtained (+557%); (4) aggregated impact factor (+109%); (5) median impact factor (+38%); (6) aggregated immediacy index (+107%). See Table 1.3 to follow the evolution of such parameters year per year. It is clear that in 2011, the Subject Category Nanoscience & Nanotechnology is fully competitive, when compared to the other subject categories showing the highest subjects overlap, in terms of aggregated and median impact factor and aggregated immediacy index (Table 1.4).

Table 1.4

Comparison among the main bibliometric parameters of the Subject Category Nanoscience & Nanotechnology with the same parameters of the related subject categories, i.e. those where there is the most subjects overlap

∗See note ∗ of Table 1.3.

†See note † of Table 1.3.

‡See note ‡ of Table 1.3.

Data from Journal of Citation Reports 2011.

From the data reported in Fig. 1.1 and Tables 1.2–1.4, the tremendous editorial blow up of nanoscience and nanotechnology in the past few years is evident. However, although all parameters are still rising, in the last three years, their second derivatives versus time seem to be negative, suggesting that we are approaching the asymptotic values for these parameters. The editorial blow up mirrors the efforts produced worldwide in the laboratories. This research is funded with public and private money and represents the expectation that the society has in respect to this new branch of science [1].

2 Heterostructures and Nanostructures: Definition and Applications, from Optoelectronic to Catalysis

On a historical ground, the future birth of nanotechnology was probably first foreseen by physicist Richard Feynman at the American Physical Society meeting at Caltech on December 29, 1959, with his famous talk There’s Plenty of Room at the Bottom.

The first applications of nanotechnology were probably semiconductor heterostructures and nanostructures, also defined as low-dimensioned systems, i.e. systems that are confined in one, two or three spatial dimensions, resulting in 2D, 1D and 0D systems, respectively [1–8]. In the community of solid-state physics and optoelectronic, 2D, 1D and 0D systems are usually labeled as quantum wells, quantum wires and quantum dots (or boxes), respectively.

However, the interest in low-dimensioned systems is not restricted to the fields of solid-state physics [1,7,9–12], interface physics [13–17], optoelectronic [7,18–24], optics and photonics [22,25,26], but examples of application of confined systems can be found also in several fields such as metallurgy [27–29], chemistry [30–60], chemical sensors [61], catalysis [62–75], photocatalysis [76–86], drug-delivery [87–95] and biomedical applications in general [26,96–100], etc. All these systems are generally labeled as nanostructures since the confinement usually lies in the nanometer scale. The single-molecule device, all along considered as the ultimate frontier in nanotechnology, has recently been reached [101–117].

Emblematic among the fields mentioned so far is the case of catalysis. Catalysis is the science that is aimed to increase the speed and the selectivity of a given chemical reaction. A catalyst is a species that allows to reducing the activation barrier of a chemical reaction, being unchanged at the end of the process. Most of the known heterogeneous catalysts are intrinsically nanostructured systems [73,118,119]. We can so affirm that catalysis is one of the branches of science that can be classified as nanoscience since its beginning. Actually, only recently, the scientists involved in the field of catalysis have explicitly used the word nano in their articles and books [73], but it is evident that people working in the field of catalysis did nanoscience since decades.

Two families of nanostructured catalysts will now be briefly mentioned. The first one concerns gold. Bulk gold is known to be chemically inert and gold jewels have been passed on through millenaries, still keeping a perfect conservation. However, when small enough particles are considered, with particle diameters below 10 nm, they turns out to be surprisingly active for many chemical reactions [66,74,75,120–122], such as for instance CO oxidation and propylene epoxidation.

As a second example, we will mention the family of nanostructured porous materials. This is the field of zeolites [31,123] and zeotypes [124,125] that are nanoporous crystalline systems constituted by corner-sharing [TO4] tetrahedra (T = Si, Al or P mainly) exhibiting pores of molecular dimension (0.5–1.5 nm range). Pertinent is also the class of mesoporous materials [126], being amorphous aluminosilicates having regular pores distribution in the 1–10 nm range. These are the classes of materials that, starting from the late 1970s, entered aggressively in the market of catalysts used in industrial plants. Such materials acts as nanoreactors since the chemical reactions occur inside their cavities. The pore opening and the dimension of the internal cavities discriminate the reactant molecules able to reach the catalytic centers and the product molecules able to be formed. We are so dealing with shape-selective catalysts that represent the best artificial attempt to simulate the enzymes created in the nature.

The possibility of tuning framework porosity, topology as well as framework compositions is the main reason why zeolites and zeotypes became the most successful materials for a broad range of applications like gas adsorption and separation and catalysis [31,73,127–132]. However, between 2000 and 2010, the role of zeolites as the leading class of crystalline porous materials has been challenged by a new emerging class of porous materials: metal organic frameworks (MOFs) [42,133–144]. MOFs diverge from zeolites in important ways [46,145]. The most important one being their larger diversity and flexibility in composition and less-topological constraints in the formation of the porous lattices. The enormous number of new MOF frameworks reported every year reflects this flexibility and the large interest for their potential applications. Zeolites are restricted to tetrahedral [TO4] networks, whereas the inorganic cornerstone in MOF topologies allow a much greater flexibility, include e.g. single metal atoms or cluster of coordinated metal atoms (with tunable level of complexity) or extended inorganic substructures extending in one, two or three dimensions [146]. It becomes so evident that MOFs will be able to host in their cavities amazing nanoscience in the next future.

3 Dynamic Interplay among Growth/Synthesis Techniques, Theoretical Modeling and Characterization Techniques in the Design and Improvement of Semiconductor Heterostructure-Based Devices

Great efforts have been made in improving the preparation methods of low-dimensioned systems in order to optimize the size control of the confinement regions and of the confined systems able to guarantee a spatial homogeneity, and to optimize the preparation reproducibility: epitaxial growth [147–167], etching/regrowing [5,168,169], self-organized growth [170–172], Langmuir–Blodgett films [32,33,173–176], top-down nanolithography [56,177–188], scanning tunneling microscopy (STM) tip-assisted deposition [163], surfactant assemblies as supramolecular templates [189], bottom-up self-assembly approaches [56,163,171,190–198], intrazeolite encapsulation [30,31,33,34,56,199–206], etc. On the parallel sides, important theoretical efforts have been made to predict the properties of low-dimensioned systems and relevant progresses have been achieved in their characterization [21,181,207–221].

Improvements in the realization of nanostructures can be realized by a tight interplay among the progress achieved on these three grounds, as basically schematized in the flow chart reported in Fig. 1.2 and described in the following. (i) Theoretical calculations predict the physical properties of a given nanostructure; (ii) the preparation techniques try to realize it; (iii) structural characterization techniques check whether the actually realized nanostructure corresponds to the desired one or not; (iiia) if not, the preparation conditions have to be optimized and step (ii) has to be repeated; (iiib) if yes, then optical, electrical, electronic, chemical reactivity, etc. properties are checked to verify whether the desired nanostructure has actually the foreseen properties (iv); (iva) if not, then the level of theory used in step (i) has to be improved and the game has to restart again from the beginning; (ivb) if yes, then the end of the story. Point (ivb) represents the final point of the scientific work and the future of the device lies now on an engineering/economical level, where the production rate, the realization costs and the demand of the device are the main driving forces. Of course, the interplay often moves in the opposite direction, i.e. theoretical models help in the interpretation of previous nonunderstood (or wrongly interpreted) experimental results.

Figure 1.2 Flow chart schematizing the strictly interconnected interplay among theoretical calculations (i), synthesis/growth techniques (ii) and characterization techniques (iii and iv), aiming to the realization of nanostructures with desired performances.

4 Purposes of the Book and Chapters Layout

As was the case for the first edition, the second edition of the book Characterization of Semiconductor Heterostructures and Nanostructures is structured in chapters, each one devoted to a specific characterization technique used in the understanding of the properties (structural, physical, chemical, electrical, etc.) of semiconductor quantum wells, superlattices and nanostructures in general. One chapter is devoted to the ab initio modeling. The book has basically a double aim. The first one lies on the educational ground. The first part of each chapter provides the basic concept of each of the selected techniques at a level easily accessible to master and PhD students in Physics, Chemistry, Material Science, Engineering, Nanotechnology. The second aim is to provide a selection of examples from the recent literature of the top results obtained with the specific technique in understanding the properties of semiconductor heterostructures and nanostructures. Each chapter has this double structure: a first part devoted to explain the basic concepts, providing the larger possible audience, and a second one to the discussion of the most peculiar and innovative examples, allowing the book to have the longer possible life time. Of course, the book is devoted to the specialized subset of scientists working in the field of design, growth, characterization and testing of heterostructures-based devices in both academic and industrial laboratories. But the final goal is somewhat more ambitious, and in this regard, the topic of quantum wells, wires and dots should be seen as a pretext of applying top-level characterization techniques in understanding the structural, electronic, etc. properties of matter at the nanometer (even subnanometer) scale. In this way, it is aimed to become a reference book in the much broader, and extremely hot, field of Nanotechnology.

Except for growth and synthesis techniques, step (ii) of the flow chart in Fig. 1.2, for which we suggest to refer to specified books and review articles [5,30–34,56,147,160–162,170–174,179,189,190,196,222–233], all the remaining three fundamental steps of the flow chart reported in Fig. 1.2 have been considered in the book. Chapter 2, coordinated by Maria Peressi (University of Trieste, Italy), is devoted to the study of structural and electronic properties of semiconductor heterostructures and nanostructures by ab initio calculations, step (i) in Fig. 1.2.

The experimental investigation of structural properties step (iii) in Fig. 1.2 is treated in Chapter 3 discussing X-ray diffraction (XRD), coordinated by Claudio Ferrari (IMEM-CNR, Parma, Italy); Chapter 4 dealing with surface sensitive X-ray techniques, anomalous scattering and coherent diffraction imaging, coordinated by Tobias Schülli (ESRF, Grenoble, France); Chapter 5, focusing on the structural investigation of matter at a larger distance scale, with small-angle X-ray scattering (SAXS), written by Alessandro Longo (CNR-Palermo Italy) and Giuseppe Portale (Netherlands Organization for Scientific Research and DUBBLE beamline at the ESRF); Chapter 6 dealing with X-rays and neutrons total scattering, coordinated by Simon J. L. Billinge (Columbia University, New York, USA); Chapter 7 introducing X-ray absorption spectroscopies (XAS), authored by Federico Boscherini, (University of Bologna, Italy); Chapter 8 treating the coupled crystallographic and spectroscopic DAFS technique, written by Maria Grazia Proietti, (CSIC-Universidad de Zaragoza, Spain) and by Hubert Renevier (CEA Grenoble, France); Chapter 9, describing the XRD, X-Ray Fluorescence (XRF) and XAS techniques based on micro and nanofocused X-ray beams, coordinated by Gema Martinez-Criado (ESRF, Grenoble, France); Chapter 10, presenting transmission electron microscopy (coordinated by Laura Lazzarini IMEM-CNR, Parma, Italy); and Chapter 11, introducing atomic force microscopy (AFM) and STM, written by Ch. Manfredotti (University of Turin, Italy).

Coming to the characterization of the nanostructures properties, step (iv) in Fig. 1.2, they are treated in the following chapters: Chapter 12 (coordinated by Stefano Sanguinetti, Universita Milano II, Italy), and Chapter 14 (coordinated by Giancarlo Salviati, IMEM-CNR, Parma, Italy) are devoted to photoluminescence and cathodoluminescence and electron photoemission spectroscopies, respectively. The methods for investigating the electronic properties of semiconductor nanostructures are discussed in Chapter 14 authored by Giorgio Margaritondo, EPFL, Lausanne, Switzerland), where the band discontinuities in semiconductor heterojunctions are also discussed. Chapter 16, coordinated by Lorenzo Rigutti (University Paris Sud, Orsay, France), deals with the electrical properties of nanostructures; Summarizing, this volume reports the competent contributions of an international team of scientists affiliated to important laboratories and universities in Italy (23), France (8), United States (3), Belgium (2) and in Belgium, Japan, The Netherlands, Spain, and Swiss (one each).

By moving from bulk materials down to 2D-, 1D- and 0D-confined heterostructures, the volume (and thus the number of atoms) forming the active regions in nanostructured devices is reduced by several orders of magnitude. This means that the understanding of the structural properties of such nanostructures often requires high photon flux techniques like those provided by synchrotron radiation sources [233–237]. In fact, synchrotron radiation has distinct advantages as a photon source, notably high brilliance and continuous energy spectrum; by using the latter characteristic, atomic selectivity can be obtained and this is of fundamental importance to investigate the structural environment of atoms present only in a few angstrom (Å) thick interface layers of heterostructures [21,238,239]. The third-generation synchrotron radiation sources have allowed to reach the limit of measuring a monolayer (or even submonolayer) of material, corresponding to about 10¹⁴ atoms/cm² [240]. Chapters 4–9 and 14 describe synchrotron radiation techniques. Chapter 6 introduces the benefits of total scattering experiments performed with neutron sources.

The first edition of the book Characterization of Semiconductor Heterostructures and Nanostructures was edited by Elsevier in 2008 (ISBN: 978-0-444-53099-8). In 2010, Elsevier reprinted the book for the Chinese market (ISBN: 978-7-03-026969-0). The impressive evolution of the fields related to nanotechnologies, together with the relative good editorial success of the first edition of the book, justified the need to publish a second edition. The first edition was structured on 13 chapters, each one devoted to a specific characterization technique. All the 13 chapters constituting the first edition are still present in the second, although in a slightly different order. With the only exception of the chapter reporting the electrical characterization (where L. Rigutti replaces A. Cavallini) and of the chapter related to surface diffraction (where T. Schülli replaces T. Metrger), the remaining 11 chapters of the first edition are leaded by the same corresponding authors. All these chapters have been deeply revisited and updated in both examples and quoted bibliography. To cover overlooked areas, four new subjects are presented in the second edition dealing with SAXS, total scattering, X-ray micro- and nanobeams, and AFM/STM in chapters 5, 6, 9 and 11, respectively. The book is now able to better describe the most relevant, powerful and recent characterization techniques used in the study of nanostructured materials.

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¹Subject Categories are classes where journals are sorted according to the scientific topic of the published papers.

Chapter 2

Ab initio Studies of Structural and Electronic Properties

Maria Peressi¹,² and Alfonso Baldereschi¹,²,³, ¹Department of Physics, University of Trieste, Strada Costiera 11, I-34151 Trieste, Italy, ²CNR-IOM DEMOCRITOS National Simulation Center, Trieste, Italy, ³Institute of Theoretical Physics, École Polytechnique Fédérale de Lausanne (EPFL), CH-1015 Lausanne, Switzerland

Contents

1. Introduction

2. Basic Models for Band Alignments

3. Computational Approach

3.1. First-Principles Self-Consistent Calculations

3.2. Modeling Heterostructures and Nanostructures with Supercells

3.3. Predicting Structural Properties

3.4. Predicting Electronic Properties: Band Structure Alignments, Density of States, and STM Images

3.5. Linear Response Theory

4. Band Offsets

4.1. Lattice-Matched Semiconductor Interfaces

4.2. Strained (Lattice-Mismatched) Semiconductor Interfaces

4.3. Ideal and Nonideal Interfaces (Relaxations, Disorder, Interdiffusion, Defects)

5. Designing Heterostructures and Engineering Band Offsets

5.1. Bulk Strain and Composition

5.2. Interlayers

6. Electronic States

6.1. Localized Interface States

6.2. Simulating Cross-Sectional STM Images for Characterization

7. Complex Heterostructures for Advanced Applications

7.1. Semiconductor Heterostructures for Spintronic Applications

7.2. Oxide and Complex Oxide–Semiconductor Heterostructures

7.3. Semiconductor Heterostructured NWs

8. Summary and Future Perspectives

Acknowledgments

References and Notes

1 Introduction

In the past decades, computer simulations have emerged as a fundamental and powerful new tool for condensed-matter research. Simulations not only make possible the detailed interpretation of experimental results, particularly at the atomic scale, but in most (actually the most interesting) cases also they provide predictions of properties and processes not yet observed in the laboratory. They are also extremely useful in the accurate assessment of existing theories and models and often they provide the inspiration for new ones (see the discussion reported in section 3 of chapter 1).

It is possible nowadays to study the structural and electronic properties as well as the energetics of many-electron systems by performing fully ab initio computations, that is, by solving the quantum-mechanical equations for the system under consideration without any use of empirical parameters or experimental inputs. For further details, we refer the reader to recent books providing an extensive exposition of theory and methods for electronic structure calculations [1–3], also peculiar to nanostructures [4]. This chapter will focus on one of the most efficient and widely used ab initio methods, a method based on the density-functional theory (DFT) and making use of pseudopotentials to describe the valence electrons.

Ab initio simulations at the nanoscale cover a large variety of systems that can be classified according to their reduced dimensionality: surfaces and films (2D), nanotubes and nanowires (NWs; 1D), clusters, nanoparticles, and quantum dots (0D). At the nanoscale, new phenomena come into play, such as tunneling, fluctuations, confinement, and discreteness.

A wider variety of systems and further new physics come into play when materials are interfaced, thus forming heterostructures. For the sake of clarity, we refer to heterostructures where the interface between the two building blocks is well defined at the atomic scale. Heterostructures can be obtained joining materials extended in 2D (junctions in case of two semi-infinite materials; quantum wells and superlattices, for slabs of nanoscopic thickness); we refer to nanoheterostructures when the extent of one or more of the phases being separated by the interfaces is nanoscopic (it is for instance the case of radial core–shell NWs). Heterostructures, in general, can be characterized joining materials similar or different for their structure, lattice parameter, and chemistry, with increasing degree of complexity. When the materials share the same structure and the same lattice parameter, it is the very peculiar case of lattice-matched heterostructures, the prototypical example being GaAs/AlAs. At variance, we refer to lattice-mismatched heterostructure if the constituent materials share the same structure but a different lattice parameter, as in most cases, since only a few semiconductors have a common lattice parameter. See section 2 of chapter 3 for having an overview on lattice-mismatch from the diffraction point of view. More complicated is the case when the materials have a different crystalline structure (for instance, zincblende and wurtzite), or even different solid phases (crystalline/amorphous). Heterostructures can be classified also according to the chemical mismatch of the constituents: We distinguish between isovalent and heterovalent heterostructures, according to whether the atoms across the interface in the same crystalline sublattice have the same valence (interfaces made of semiconductors of the same group) or different valence (semiconductors of different groups). Changing also only one of the constituents, the properties of the heterostructure may completely change. Although surfaces could be simply considered as an interface with vacuum, new physics come into play, and their treatment would require special consideration. We will not discuss them further.

All the above-mentioned systems (2D, 1D, 0D nanostructures, and heterostructures) can be afforded by ab initio calculations; according to the degree of complexity, the simulation cells could be smaller or larger, containing from a few to hundreds of atoms, but the approaches and the main technical details are similar. For the sake of definiteness and clarity, in this chapter, we focus our attention on heterojunctions between two semi-infinite materials, involving 2D interfaces. To show an example of the application of the ab initio method to a different geometry, we will briefly discuss in Section 7.3 the case of semiconductor core–shell heterostructured NWs.

In the case of semiconductor heterostructures, numerical simulations have been essential in establishing general trends in the electronic properties, and in particular the band-structure discontinuities at interfaces. An important issue that has been addressed and rationalized is whether the band discontinuities are intrinsic or not, that is, whether they are determined solely by properties of the constituent bulk materials and hence display commutativity and transitivity, or they also depend on interface-specific features, such as crystallographic orientation and abruptness, and are therefore tunable to some extent. Although simple models and semi-empirical methods have been particularly helpful in understanding the broad features of experimental results, the solution of such a difficult issue has required ab initio simulations able to incorporate atomic-scale details and quantum effects.

After a brief presentation of some basic models for band alignments (Section 2), we give a general description of the computational approach and specific tools devoted to the problem of heterostructures in Section 3, together with the most recent developments of first-principles approaches. We will then present some selected applications to the problem of band alignments (Section 4) starting from the simple and paradigmatic case of ideal GaAs/AlAs and considering also more complex cases such as strained heterojunctions, defected interfaces, alloy-based heterostructures, and crystalline/amorphous interfaces. We will discuss also band-offset engineering (Section 5), which has been the subject of an intense theoretical effort in order to both understand underlying phenomena and predict offset modifications. Section 6 is devoted to the investigation of the electronic states, such as localized interface states, whose presence is often invoked to interpret anomalous features in the results of photoemission spectroscopy (see chapter 14), optical and transport measurements (see chapters 12 and 15, respectively), and imaging of the local density of states (LDOS) using scanning tunneling microscopy (STM, see chapter 11), which, originally used for surface analysis, can also be employed to characterize semiconductor interfaces when used in cross-sectional geometries. Finally, in Section 7, we will address some properties of semiconductor-based heterostructures, which are nowadays of particular technological interest in magneto-opto-electronic devices, such as those with magnetic materials for spintronic applications, with oxides and complex oxides, and heterostructured NWs.

2 Basic Models for Band Alignments

For a description of the experimental approaches used to measure semiconductors band alignment, the reader should refer to chapters 12, 13, 14 of this book, devoted to photoluminescence, cathodoluminescence and photoemission spectroscopies, respectively. Theoretical and numerical investigations based on different approaches have contributed to predict band-offset values and to identify the basic mechanisms responsible for band-structure alignments. Successful investigations can be divided into two main classes: (1) models (some examples are given in this section) and approaches making simplifying and sometimes even drastic approximations in the description of the interface, but retaining the most relevant physical concepts, and (2) accurate computational studies based on self-consistent ab initio approaches, in which interface features such as orientation, stoichiometry, abruptness, and defects are taken into full account.

The focus of this chapter is on the latter approach since it has played a major role in understanding the physical mechanisms governing band discontinuities and in providing accurate predictions. However, we mention in this section some simple basic models that have the merit of having addressed the problem, helped in understanding relevant factors, and provided a first predictive tool. For a wider overview and details, we address the reader to books [5,6], containing also original papers of early works, and reviews [7–9].

The root of the band-offset problem is that the average of the electrostatic potential in an infinite solid is an ill-defined quantity [10] and therefore no universal energy scale exists to which the band structures of different semiconductors can be easily and uniquely referred. The lineup of the average electrostatic potential across the interface between two semi-infinite solids is, on the contrary, well defined and band-edge offsets are obtained by adding to it the bulk band-edge difference resulting when the arbitrary values of the electrostatic potentials in the two materials forming the interface are aligned. The latter quantity is easily obtained from band-structure calculations of the two bulk materials and the difficulty resides in accurately predicting the lineup of the average electrostatic potential across the interface which contains all the effects of interface-specific phenomena. Band-offset models differ from each other in the method they propose for approximating the average electrostatic-potential lineup without performing any complicated analysis of interface processes. Most models are based on intrinsic reference levels that are defined for each material individually.

This is the case of the historical electron-affinity rule proposed by Anderson [11] in which the offset of the conduction-band minimum is set equal to the difference in electron affinities of the two materials. This rule is an extension of the famous Schottky–Mott model [12,13] for predicting Schottky barrier heights at metal–semiconductor junctions. The Anderson model was generally accepted until the late 1970s, although it is based on the assumption, not justified, that the electron affinity of the two surfaces forming the interface remain unchanged on forming the contact. Later, Van Vechten proposed to use bulk electron affinities, defined in the context of the dielectric theory of electronegativity and neglecting any surface specific terms [14,15].

Harrison [16,17] calculated within a tight-binding approach the valence-band maxima for all tetrahedral semiconductors, referred to the energy levels of neutral atoms in vacuum. The offsets, obtained directly by differences, are reliable on the scale of a few tenths of 1 eV.

Frensley and Kroemer [18,19] choose the so-called average interstitial crystal potential, defined as the average electrostatic potential at the midpoint between adjacent atoms, as the reference level for the band structure of each individual semiconductor. The lineup across the interface between the two average potentials is estimated with a model distribution of point charges on the atoms and results in a dipole shift that can be expressed in terms of electronegativity differences, that is, differences between bulk quantities of the two materials forming the interface.

Other theories focus on the concept of charge neutrality level (CNL) in semiconductors. For a given semiconductor, the CNL is defined as the energy level in the bandgap below which interface charges are canceled out by the lack of states in the semiconductor valence band. The CNL is a characteristic of the semiconductor and the specific position in the gap depends on the interface. The CNLs of two semiconductors in general do not coincide and, on forming the junction, electron charge will flow across the interface toward the alignment of the neutrality level [20] that, however, will have a residual mismatch due to finite dielectric screening of the semiconductors [21]. Band-structure discontinuities can then be obtained in a zeroth-order approximation by the exact alignment of the two levels or, in a better approximation, by estimating their mismatch on the basis of the dielectric properties of the interface, as done for instance by Harrison and Tersoff [22], using a tight-binding approach. Cardona and Christensen [23] used the semiconductor’s midgap energy as energy reference and hydrostatic deformation potentials to evaluate band offsets.

The concept of intrinsic CNLs works well for ideal, lattice-matched, nonpolar interfaces such as for instance GaAs/AlAs, where it predicts a negligible dependence of band offsets on the crystallographic orientation of the interface, in good agreement with experimental data and self-consistent calculations [24]. However, in several cases, such as polar interfaces, band offsets depend considerably on orientation and other interface details. To account for this dependence, Flores and coworkers [25] introduced the concept of extrinsic CNLs depending on interface geometry.

In the late 1970s, self-consistent calculations based on semi-empirical pseudopotentials started to be performed not only for bulk materials but also for supercells modeling heterojunctions, as for instance in the pioneering works by Baraff et al. [26] and Pickett and Cohen [27,28]. The problem of heterojunctions could thus be approached theoretically in a more rigorous way and the way was open to the modern full ab initio supercell calculations that will be discussed in detail in the remaining part of the chapter. At the same time, ab initio calculations suggested the formulation of more refined, parameter-free models. Different models adopt different reference levels, deep (atomic-like) core levels or local electrostatic potentials.

Through all-electron first-principles electronic structure calculations of core levels, Wei and Zunger systematically calculated the natural band offsets between several II-VI and separately between III-V semiconductor compounds. They found that the valence-band offset (VBO) in common-anion systems is primarily determined by intrinsic bulk effects and that interface charge transfer has a small effect on these quantities, provided that cation d orbitals are correctly taken into account [29–31]. A revised model to calculate the natural unstrained band offsets between all group IV, III–V, and II–VI semiconductor compounds has been recently proposed, using an all-electron band-structure approach and taking into account the deformation potential of the core states [32].

Van de Walle and Neugebauer studied the electronic transition level of hydrogen in a wide range of semiconductors and insulators, that is, the Fermi-level position where H+ and H− have equal formation energy. They propose a universal alignment of this level, which can be considered as a reference level to fix the position of the band structure of unstrained semiconductors and insulators on the same absolute energy scale. Calculating the electronic transition level of hydrogen with respect to the topmost valence band of each semiconductor, the natural band offsets can be obtained by difference. Effects of strain or dipoles at realistic interfaces can be also included [33].

Among the more refined models based on first-principles calculations, we mention the model-solid approach proposed by Van de Walle and Martin [34,35]. The electron charge distribution of both bulk semiconductors and heterostructures is well described by the superposition of the neutral, spherical atomic densities, calculated in detail for atoms in vacuum. Deviations are generally small, due to electron density readjustments associated with the formation of bonds. The reference energy for each material is the average (pseudo)potential in a model solid, in which the charge density is constructed as a superposition of these neutral, spherical (pseudo)atomic densities. The bulk band structures of the two semiconductors are then aligned according to these average potential positions. This model has been successfully applied to a large class of lattice-matched heterojunctions and later extended to the case of strained heterojunctions [36]. The model-solid approach has been widely used for quantitative predictions of band offsets at semiconductor interfaces [37–39]. Care should be taken in applying the approach to strongly ionic semiconductors whose electron charge density is less accurately reproduced by a superposition of neutral atomic densities than that of strongly covalent materials.

On lines similar to those of the model solid, Baldereschi et al. have proposed a model based on an accurate description of the electron charge density in heterojunctions in terms of neutral building blocks derived from the two bulk constituents [40]. For lattice-matched common-anion (common-cation) heterojunctions, the building blocks are the charge densities within Wigner–Seitz cells centered on the cations (anions) and do not have any net charge or dipole or quadrupole. Equivalently, one can consider building blocks containing the average charge density of the two bulks, and others containing one half of the charge-density difference and taken with the plus or minus sign on one side or the other of the interface, respectively. The electrostatic-potential lineup across the interface is orientation independent since it depends only on the difference between the charge distributions of the building blocks. This Wigner–Seitz charge-density model is very accurate but applies to lattice-matched systems only.

The formulation of the model, however, pointed out what is relevant to the band alignment problem, that is, differences between the charge distributions of the two constituting materials, which typically are quite small with respect to density variations in the bulk of a semiconductor, and can be calculated accurately with a low-order perturbation approach. In general, when the two constituent semiconductors are rather similar to each other, their heterojunction can be viewed as a perturbation with respect to an appropriate reference periodic system: the perturbation being related to the potential difference between different ionic cores on the two sides of the interface. The response, to the lowest order, is a charge-density linear response of the reference periodic system to the potential perturbation, so that it is possible to derive macroscopic quantities, such as the electrostatic-potential lineup