One challenge of working on hybrid halide perovskites is that the field is moving so rapidly. A second is that there are just too many publications. A third is that many of the older papers use different nomenclature so that it can be difficult to discover them. I started a Mendeley group to track papers, and I think we have done a decent job on the older literature (especially in the key work from the 1980s and 90s). In 2014, there were over 400 publications on CH3NH3PbI3, and there are likely to be over 1000 in 2015 alone, so it is almost impossible to absorb all available information.
From a Web of Science search for “hybrid perovskite OR MAPI OR CH3NH3PbI3 solar cell” with 1564 results – 28th May 2015
Here is a suggested reading list to get started:
1. Dynamic disorder in methylammoniumtrihalogenoplumbates (II) observed by millimeter‐wave spectroscopy (Journal of Chemical Physics, 1987) – Weber reported methylammonium lead iodide in 1978, but the interesting characterisation started here, with the first evidence for disorder due to molecular dipoles.
2. Calorimetric and IR spectroscopic studies of phase transitions in methylammonium trihalogenoplumbates (Journal of Physics and Chemistry of Solids, 1990) – The PhD thesis of Noriko Onoda-Yamamuro is a gold-mine of useful information and careful measurements. It began with a report of the heat capacity and IR spectrum.
3. Conducting tin halides with a layered organic-based perovskite structure (Nature, 1994) – David Mitzi kickstarted interest in the optoelectronic properties of organic-inorganic perovskites beginning here and publishing another 30 or so papers in the following decade.
4. Templating and structural engineering in organic–inorganic perovskites (Dalton Transaction, 2001) – Back to David Mitzi for a review on the chemical and structural diversity of this family of compounds.
5. Organometal Halide Perovskites as Visible-Light Sensitizers for Photovoltaic Cells (JACS, 2009) – The first solar cell from Japan, but note the substantial effort that had been put into developing these materials in advance.
6. Efficient Hybrid Solar Cells Based on Meso-Superstructured Organometal Halide Perovskites (Science, 2012) – The first high-efficiency solid-state solar cell from Henry Snaith FRS and the point in time when the world took notice.
7. Atomistic Origins of High-Performance in Hybrid Halide Perovskite Solar Cells (Nano Letters, 2014) – Essentially a think piece, trying to link experimental observations with theory, and the first suggestion that lattice polarisation is important for the photovoltaic action.
8. Compositional engineering of perovskite materials for high-performance solar cells (Nature, 2015) – Things have progressed since 2012 with solar cells made with a variety of materials in a range of architectures. Sang Il Seok’s group hold the record and it is with the complex formulation of meythlammonium/formamidinium – lead – iodide/bromide.
I wouldn’t recommend to start with reading about device hysteresis. While the case is almost closed in my opinion, there is no definitive publication yet (just plenty of data and speculation).
Life was comfortable back in 2007. While starting to work on quaternary semiconductors for thin-film solar cells, there was very little literature. It was possible to read all of the papers in the field. Since the report of a 10% efficient solar cell made from Cu2ZnSn(S,Se)4 in 2010, interest in the field exploded and there now stands over 1000 publications. I feel sorry for any new graduate student beginning a project…
From reading quite a few of these papers and attending conferences and workshops over the years, here is a decent reading list to get started:
1. Development of CZTS-based thin film solar cells (Thin Solid Films, 2009) – An important historical overview of the development of the field. Like many technologies, it all started in Japan.
2. New routes to sustainable photovoltaics: evaluation of Cu2ZnSnS4 as an alternative absorber material (Physica Status Solidi B, 2008) – An important paper from Jonathan Scragg (whose PhD thesis turned into the first book on kesterite solar cells) with layers made by electrodeposition.
3. The crystal structure of kesterite type compounds: A neutron and X-ray diffraction study (Solar Energy Materials and Solar Cells, 2011) – X-ray diffraction has trouble distinguishing between Cu and Zn. Neutron diffraction confirms the ground-state crystal structure (not stannite) and the tendency for cation disorder.
4. Kesterite Thin-Film Solar Cells: Advances in Materials Modelling of Cu2ZnSnS4 (Advanced Energy Materials, 2012) – The complexity of these materials has provided a fertile ground for theory and simulation, with early efforts reviewed here on structure, defects and band energies.
5. 8.6% Efficient CZTSSe Solar Cells Sprayed from Water–Ethanol CZTS Colloidal Solutions (Journal of Physical Chemistry Letters, 2014) – simple, clean and easy to scale up, with more recent reports of reproducible 10% efficiency from this approach.
6. Device Characteristics of CZTSSe Thin-Film Solar Cells with 12.6% Efficiency (Advanced Energy Materials, 2014) – The current record device with 12.6% efficiency. The one to beat!
7. Influence of compositionally induced defects on the vibrational properties of device grade Cu2ZnSnSe4 absorbers for kesterite based solar cells (Applied Physics Letters, 2015) – Precision Raman spectroscopy is becoming increasingly useful for identifying secondary phases and quantifying structural disorder in kesterites. The team at IREC are leading the way.
8. Suns-VOC characteristics of high performance kesterite solar cells (Journal of Applied Physics, 2014) – What is limiting performance to less than 20%? This is one of several important detailed charactertisation papers that point to issues with the back contact.
There have been discussions regarding hysteresis in the performance of hybrid halide perovskite solar cells since the MRS Fall Meeting in 2013 (a brave presentation from the group of Mike McGehee and supplementary slides from the presentation of Henry Snaith). Since then, there has been a flurry of papers reporting and attempting to characterise the behaviour (see a news piece in Chemistry World this week).
A related phenomenon is the low frequency dielectric dispersion of these materials (mentioned in my recent stream of consciousness), where large polarisation features emerge due to build up of charge (e.g. see the Maxwell-Wagner effect).
This effect reminded me of some arugments in the literature several years ago regarding the characterisation of ferroelectric materials (from Bananas go Paralectric to Ferroelectrics go Bananas). The response observed for a banana is remarkably similar to the “giant dielectric effect” reported for the (inedible) hybrid halide perovskites. Quite a chunk of literature can be rationalised through this anology: “With simple experiments, the response of a banana to electric fields is revealed as characteristic for an inhomogeneous paraelectric ion conductor.”
Food for thought…
For research, 2014 has been an extremely fun year. There have been many new projects going in unexpected directions, which keeps things fresh and interesting. My research group composition has been changing too (Out: Lee to Kytoto, Davide to Oxford and Rachel to Queen Mary; In: Suzy from York, Ruoxi from Fudan, Katrine from Aarhus), which alters the dynamic. There is no such thing as a quiet or normal week.
Publications from 2014:
- Automated procedure to determine the thermodynamic stability of a material and the range of chemical potentials necessary for its formation relative to competing phases and compounds
- Electronic structure and band alignment of zinc nitride, Zn3N2 (OA)
- From kesterite to stannite photovoltaics: Stability and band gaps of the Cu2(Zn,Fe)SnS4 alloy (OA)
- N incorporation and associated localized vibrational modes in GaSb
- Prediction of Electron Energies in Metal Oxides (OA)
- Three-electron two-centred bonds and the stabilisation of cationic sulfur radicals (OA)
- Crystal electron binding energy and surface work function control of tin dioxide
- Defect chemistry of Ti and Fe impurities and aggregates in Al2O3 (OA)
- Computational screening of structural and compositional factors for electrically conductive coordination polymers (OA)
- Relativistic quasiparticle self-consistent electronic structure of hybrid halide perovskite photovoltaic absorbers
- Ultra-thin oxide films for band engineering: design principles and numerical experiments
- Ab initio thermodynamic model of Cu2ZnSnS4 (OA)
- Atomistic Origins of High-Performance in Hybrid Halide Perovskite Solar Cells (OA)
- Thermal physics of the lead chalcogenides PbS, PbSe, and PbTe from first principles
- Origin of deep subgap states in amorphous indium gallium zinc oxide: Chemically disordered coordination of oxygen
- Design of I2−II−IV−VI4 Semiconductors through Element Substitution: The Thermodynamic Stability Limit and Chemical Trend
- Electronic Chemical Potentials of Porous Metal−Organic Frameworks (OA)
- Ellipsometric characterization and density-functional theory analysis of anisotropic optical properties of single-crystal SnS
- Molecular ferroelectric contributions to anomalous hysteresis in hybrid perovskite solar cells (OA)
- Identification of critical stacking faults in thin-film CdTe solar cells
- Stacking-dependent energetics and electronic structure of ultrathin polymorphic V2VI3 topological insulator nanofilms
- Ligand design for long-range magnetic order in metal–organic frameworks (OA)
- Transferable Force Field for Metal−Organic Frameworks from First-Principles: BTW-FF (OA)
- Tunable Trimers: Using Temperature and Pressure to Control Luminescent Emission in Gold(I) Pyrazolate-Based Trimers (OA)
- Electronic Structure Modulation of Metal−Organic Frameworks for Hybrid Devices (OA)
We have done better for fully open access (OA) publications this year, but still room for improvement. Generally, we don’t pay for gold open access with the American Physical Society (e.g. Physical Review B or Physical Review Letters) because they have the most generous policy for hosting on personal websites and institutional databases.
[fade to black and white] I remember hunting down a series of 1950s papers on sterochemical lone pairs by L. E. Orgel at the start of my PhD. There was the wonderful satisfaction of finding the right volume of the journal, photocopying the paper, and then curling up in the corner of the library basement to read it. If I started this year, a quick web search just sends me to the right place.
Immediate access to information is useful, but it makes it increasingly difficult to navigate the expanding literature. Even in my general area of computational materials chemistry, there are too many journals, papers and authors to keep track of. My current workflow involves the following web services:
- Google Scholar. The commercial Web of Science and Scopus search engines are quickly becoming redundant. Google is faster and more effective. There are some nice features such as direct export to BibTeX, and access to pdfs that you may not have subscriptions to (e.g. stored on personal websites or online databases). There is also a surprisingly accurate alert system, which gives you recommended reading based on the papers you have published and cited.
- Mendeley. On one hand, Mendeley is useful for sharing papers. I use it for maintaining a list of publications in the emerging field of hybrid perovskites, for keeping track of our journal club, and an essential reading list for new students. The desktop client is also very useful for synching pdfs across machines (including notes and annotations), and for maintaining a bibliography for LaTeX or Word documents. The cite-as-you-write feature has now made Endnote redundant (which has always been a clunky and error prone piece of software). Mendeley is particularly smart at importing missing database entries when you edit a collaborator’s document.
- Old Reader. Since the early death of Google Reader, I tried out many options for tracking RSS feeds from journals in my field. Eventually, I settled with the Old Reader. As the name suggests it maintains the functionality of Google Reader. It is fast and displays TOC art quite nicely. The alternative is weekly alert emails from journals, but I enjoy my morning coffee browsing through the new articles of the day (caffeine and new science are equally addictive).
I succeeded in publishing a few single author papers in the short window between being a postdoc (working for the boss) and a faculty member (working for the group). I do love collaboration, especially when it goes beyond contributing data to shaping the narrative and presentation in a manuscript. As the average number of authors increases a linear procedure of passing successive drafts from X to Y is both inelegant and inefficient*.
I have detested MS Word since the day Clippy appeared**, so let’s disregard any progress by MS Office in the cloud. We all know real scientists use LaTeX (my cocktail is MacTeX, Texmaker and occasionally Textmate). Many social LaTeX websites have appeared, e.g. Share Latex, but they currently seem clunky in dealing with packages, libraries and figures. One DIY solution I have been using in my group is Git. It may not be perfect, but whatever works!
Git is a revision control system used in code development. We have been putting codes and scripts online using GitHub, which offers free public Git repositories. The protocol allows you to keep track of any file type, so for LaTeX it works just as well. Of course, you don’t really want to put your draft manuscripts in the public domain, but BitBucket offers unlimited free private repositories for education. The procedure is very simple***:
- Initiate the repository locally
- Create the repository online
On the BitBucket website, complete the new repository form:
- Push to the cloud!
BitBucket gives you instructions to link the new online repository to your local files. In my case (from the same directory as above):
git remote add origin email@example.com:aronwalsh/2014-02-snso.git
git push -u origin --all # pushes up the repo and its refs for the first time
git push -u origin --tags # pushes up any tags
- Write, share and maintain
Now for the easy bit: writing. Firstly, give all coauthors access to the repository. You can then simply add (or modify) files in the folder on your local machine and, when you are ready, “push” the changes to the online server. The latter can be done either using the command line or a GUI such as the one provided by GitHub or the more powerful SourceTree. Git will keep track of all changes made and you have the options to merge different versions or reject specific changes (e.g. from the author who insists on American spelling). You also have the option to ignore certain files types including all the auxiliary files generated you compile the TeX. So far, the system has been productive for me and avoids those “conflicting copy” errors that arise when using Dropbox for co-editing a manuscript. If you already use Git for software development, it is highly recommended.
*One exception to this is a very fruitful collaboration I have with Shiyou Chen at Fudan University. An 8 hour time difference can be ideal for sequential drafting.
**Okay, I occasionally have to use Word when collaborating due to its ubiquity.
***Firstly, create a BitBucket account using your university email address.
2013 was the fastest year on record (plenty done, with even more to do). Christmas is a nice time to step back and refocus. In terms of research it has been a year where my group matured to produce a series of excellent papers that wouldn’t have been possible without their combined skills (and backgrounds from chemistry, physics, chemical engineering and materials science). I am indebted to them and our many talented collaborators around the world.
Publications from 2013:
- “PbO2: from semi-metal to transparent conducting oxide by defect chemistry control“
- “Thermodynamic and electronic properties of tunable II–VI and IV–VI semiconductor based metal–organic frameworks“
- “Prediction of (TiO2)x(Cu2O)y alloys for efficient photoelectrochemical water splitting“
- “Classification of Lattice Defects in the Kesterite Cu2ZnSnS4and Cu2ZnSnSe4 Earth-Abundant Solar Cell Absorbers“
- “Electronic origin of the conductivity imbalance between covalent and ionic amorphous semiconductors“
- “Band alignment in SnS thin-film solar cells: Possible origin of the low conversion efficiency“
- “Microscopic origin of the optical processes in blue sapphire” (OA)
- “Electron excess in alkaline earth sub-nitrides: 2D electron gas or 3D electride?” (OA)
- “Dynamical response and instability in ceria under lattice expansion“
- “Band alignment of rutile and anatase TiO2“
- “Engineering the Optical Response of the Titanium-MIL-125 Metal−Organic Framework through Ligand Functionalization” (OA)
- “Electronic Structures of Antimony Oxides“
- “Limits to Doping of Wide Band Gap Semiconductors” (OA)
- “Helical frontier orbitals of conjugated linear molecules” (OA)
- “One-dimensional embedded cluster approach to modeling CdS nanowires“
- “Dielectric response of Fe2O3 crystals and thin films“
- “Oxidation of GaN: An ab initio thermodynamic approach“
- “Structural and electronic properties of hybrid perovskites for high-efficiency thin-film photovoltaics from first-principles” (OA)
- “Polymorphism of indium oxide: Materials physics of orthorhombic In2O3“
- “Synthesis, Characterization, and Electronic Structure of Single-Crystal SnS, Sn2S3, and SnS2” (OA)
One goal next year is to increase the proportion of fully open access (OA) publications. Institutional repositories are nice, but they don’t compare to direct access on a journal website.