Perovskite Scientists Win Nobel Prize in Chemistry

2023-10-05 17:11:33

On October 4, the Royal Swedish Academy of Sciences announced the 2023 Nobel Prize in Chemistry, which was awarded to three American scientists, Moungi G. Bawendi, for their contributions to the discovery and synthesis of quantum dots.

On October 4, the Royal Swedish Academy of Sciences announced the 2023 Nobel Prize in Chemistry. The Nobel Committee awarded the 2023 Nobel Prize in Chemistry to Professor Mongi G. Bavendy (Moungi G. Bawendi) of the MIT, USA. Professor Louis E. Bruce (Louis E. Brus) , Columbia University, USA, and scientist Alexei Ikimov (Alexey I. Moungi

), Nanocrystal Technologies, USA G. received his Ph.D. degree from the University of Chicago, Illinois, USA, in 1988. Professor, MIT (MIT), Cambridge, MA, USA.

Louis E. Ph. D., Columbia University, New York, USA, 1969. Professor, Columbia University, New York, USA. Ph.D. degree, Ioffe Physical-Technical Institute,

Alexei I., St. Petersburg, Russia, 1974. Among the former Nanocrystals Technology Inc.

in New York City, the Moungi G.

from the MIT of the United States, in February 2019, the efficiency of the perovskite solar cell developed by the company was certified by NREL to reach 24.2%. It became the 10th efficiency record point of perovskite solar cells;

-In September 2019, the efficiency of its developed perovskite solar cells was certified by NREL to reach 25.2%, becoming the 11th efficiency record point of perovskite solar cells;

-February 2021, Moungi G.

What is a quantum dot? In the dark, under the irradiation of ultraviolet lamp, the solution in a row of test tubes emits pure light from blue to red, which is breathtaking. So what is a quantum dot? Why do quantum dots emit such brilliant colors? Compared with a stone, a gravel is very different in volume, and its physical and chemical properties are almost the same. But things start to change when the size of the material enters the nanoscale. What

we call quantum dots, also known as semiconductor nanocrystals, are semiconductor crystal particles composed of hundreds or thousands of atoms, generally less than 20 nanometers in size. Semiconductor materials are the cornerstone of the information society, which are generally composed of crystals with repeating unit structure, and their semiconductor properties are determined by the type of repeating unit. Due to the size of quantum dots entering the nanometer scale, the number of repeating units in semiconductor nanocrystals is limited, which leads to great changes in the electronic structure of materials. Brus and Ekimov et al. Described this size-dependent phenomenon as a quantum confinement effect: the electronic structure of quantum dots changes from the continuous energy band of the bulk material (macroscopic crystal) to discrete energy levels, and the band gap gradually increases with the decrease of crystal size. At the same time, since the size of QDs is usually smaller than exciton (electron-hole pair) Bohr radius, the excitons generated by optical excitation are firmly bound in each QD, thus achieving high efficiency of radiative recombination (Fig. 2). Taking the most widely studied cadmium selenide (CdSe) quantum dots as an example, the bulk cadmium selenide is black powder, which usually has no fluorescence effect, while the cadmium selenide quantum dots synthesized in solution can achieve multi-color luminescence from blue light to red light by changing the size (Figure 1).

(2) The origin

of quantum dot research Human research on semiconductor quantum dots began about 40 years ago, by two research groups in the former Soviet Union and the United States, respectively, in " around 1980. After S. I., the former Soviet scientist Alexey I Ekimov explained the quantum size effect with the particle-in-a-box model [3] through the cooperation with theoretical physicist Alexander Efros and others on the basis of spectroscopy research. Interestingly, in order to reduce the controversy in the peer review process of academic journals in the former Soviet Union, Ekimov and Efros et al. Used the term "microcrystal" in their original paper to describe the samples they studied, ranging from micron-scale crystals close to the bulk phase to nanocrystals showing significant size dependence (the smallest sample size is close to 2.

Professor Louis Brus of Columbia University, who works at Bell Laboratories in the United States, also accidentally discovered the color change caused by the size change while studying the colloidal solution of II-VI semiconductor nanocrystals. Because of the background of the Cold War at that time, academic exchanges between the Soviet Union and the United States were interrupted by the "Iron Curtain", and Professor Brus did not have the opportunity to learn about the work of Ekimov and Efros. At that time, Brus noticed the one-dimensional confinement effect of epitaxially grown semiconductor superlattices. On this basis, based on the effective mass theory and taking into account the enhanced Coulomb interaction caused by dielectric polarization, Brus deduced the relationship between the first exciton excited state energy (E *) of quantum dots and the band gap width (Eg) of bulk materials, the size of nanocrystals (R), and the effective mass of electron holes (me, MH) [4]. That is, the famous Brus formula (Formula 1), which is included in textbooks. Then, the theory of quantum confinement effect has been successfully extended to ZnS, PbS, ZnSe and other material systems.

Although Ekimov and Brus have studied different material systems, "great minds think alike", based on their profound scientific insight, the theoretical model of quantum dot size has been preliminarily established.

(3) The development

of quantum dot synthesis chemistryQuantum dot synthesis chemistry is the basis for the vigorous development of quantum dot field: the application of modern chemical synthesis methods and ideas provides high-quality materials with diverse structures and rich properties for the whole field.

Thanks to the excellent leadership of Professor Brus and the excellent cooperative atmosphere of Bell Laboratory, the major progress of colloidal quantum dot synthesis chemistry also began in Bell Laboratory. In 1986, Louis Brus and his assistants Paul Alivisatos and Michal Steierwald started the metal-organic chemical synthesis of colloidal quantum dots. Moungi Bawendi joined the team in 1988. Later, Paul Alivisatos and Moungi Bawendi became independent PIs, joined the University of California, Berkeley, and the MIT, respectively, and initiated perhaps the two most famous research groups in the field of quantum dots, which trained many talents for the field.

Quantum dot synthesis chemistry made a breakthrough between 1990 and 1993, with the emergence of a "metal-organic-coordination solvent-high-temperature" synthesis route. This method was invented at Bell Labs and matured in Moungi Bawendi's group at MIT [5]. It uses dimethyl cadmium as cadmium source to synthesize high-quality cadmium selenide quantum dots in high temperature (about 300 degrees Celsius) and organic coordination solvent. This method is a milestone for the research of the whole quantum dot field. Moungi Bawendi shared the Nobel Prize!

This situation was broken by Professor Peng Xiaogang, a Chinese scholar, around 2000. Peng Xiaogang joined Paul Alivisatos as a postdoctoral fellow in 1994 and began independent research in the Department of Chemistry at the University of Arkansas in 1999. Based on the profound understanding of the reaction mechanism, Peng Xiaogang's research group developed a "green" synthesis route based on safe and non-toxic non-coordinating solvents using stable and readily available oxides or carboxylates as precursors [6-7]. With the development of new synthetic routes, the synthesis of quantum dots has gradually moved to laboratories all over the world and has been promoted in industry.

At the same time, the growth mechanism of quantum dots, core-shell structure engineering and surface ligand chemistry have also been widely explored by chemists. These advances in basic research have led to the gradual expansion of high-quality quantum dots from II-IV CdSe quantum dots to other types of semiconductor compounds, such as PbS quantum dots, InP quantum dots, CuInS2 quantum dots and so on .In 2015, the emergence of perovskite quantum dots broke through the limitation that quantum dots need to be synthesized at high temperature. Quantum dots can be reprecipitated in polymer matrix at room temperature or prepared in situ by taking advantage of the solubility difference caused by the ionic characteristics of perovskite, which brings new opportunities for optical applications.

Thanks to the progress of synthetic chemistry, quantum dots are still growing as a family of materials. The morphology and structure of quantum dots are increasingly regulated, and functional units with specific properties are constantly produced.

(4) The application

of quantum dots has attracted many scholars because of its rich physical and chemical properties. Through the unremitting exploration of basic research, many important frontier technologies have been formed [8]. For example, the efficient and stable luminescent properties of quantum dots make them a classic fluorescent labeling material, which is widely used in scientific research and in vitro detection in the field of biological detection and medical imaging, and promotes the development of imaging and detection technology. On the other hand, quantum dots have the characteristics of narrow emission and tunable emission color, which make them a new generation of luminescent material system in the field of display. At the same time, the applications of quantum dots in solar cells, infrared detection imaging, photocatalysis, quantum light sources and other fields have also made considerable progress.

Among them, one of the most representative applications is to combine the excellent photoluminescence performance of quantum dots with another Nobel Prize achievement, GaN-based blue LEDs, to achieve quantum dot color enhanced liquid crystal display technology. In this technology, quantum dots can convert the color of LED backlight into three primary colors of red, green and blue with high color purity, and achieve a wide color gamut beyond traditional liquid crystal display and organic LED display.

In addition to the commercialized quantum dot liquid crystal display, quantum dots have great application potential in the fields of future display, light source technology and new energy, such as:

(1) Future display: With the development of miniaturization, intelligence and flexibility of electronic devices, smart wearable devices are booming. Virtual reality applications require near-eye display devices with high color gamut, high refresh rate and ultra-high resolution, and quantum dot electroluminescence (QLED) technology is expected to have these characteristics simultaneously. With the rapid development of quantum dots and other related semiconductor materials, QLED devices that meet commercial performance standards are expected to be realized in the next 3 ~ 5 years and will be applied in future displays.

(2)

(3) Application of high-performance laser light source: Laser technology is one of the important technologies in the development of modern optics, and has important applications in space communication, measurement, gyroscope and military. The continuous tunability of the spectrum and the high efficiency luminescence performance of quantum dots are the core advantages of the next generation of new laser materials. At the same time, the low cost of synthesis and preparation of quantum dots will also actively promote the development of miniaturization and civilian use of lasers. Optically pumped lasers and electrically pumped lasers based on quantum dots are the research frontiers in this field.

(4) Application of single-photon light source: With the rapid development of quantum information and quantum communication technology, single-photon source is one of the essential components of quantum information devices. Because the single-particle quantum dot can be approximated to an ideal two-level system, it has unique advantages in the field of single-photon sources. At present, the most developed single-photon source devices are self-assembled quantum dots (QDs) prepared by epitaxial growth. With the development of solution preparation and processing technology of quantum dots, it is expected to use low-cost solution-synthesized quantum dots as single-photon sources to prepare multi-band, high-efficiency and low-cost quantum dot single-photon source arrays in the future, which will provide a new technology for quantum computing and quantum communication. Driven

by these applications, quantum dots began to enter the stage of industrialization exploration around 2002. Graduates or collaborators from MIT, UC Berkeley, Imperial College, University of Arkansas and other academic institutions have founded QD Vision, Nanosys, Nanoco and other start-ups, while Samsung has laid out the industrial development of quantum dot display at this stage. In 2013, Sony, Samsung and TCL successively launched LCD TVs with quantum dot backlighting, and more than 12 million quantum dot TVs were sold worldwide in 2022. According to the statistics of Touch Display Research Inc in the United States in 2019, more than 120 companies around the world have been engaged in the development and application of quantum dot technology.

(5) China's strength

in quantum dot research Compared with the international research in the 1980s, the domestic research in the field of quantum dots started a little later. In recent years, through unremitting efforts, Chinese scientists have made original and leading achievements in quantum dot synthesis, quantum dot light-emitting diode (QLED), quantum dot virus labeling, perovskite quantum dot display applications and other research directions. Academician Li Yadong of

Tsinghua University, Academician Li Yongfang of the Institute of Chemistry of the Chinese Academy of Sciences, Academician Wu Lizhu of the Institute of Physics and Chemistry of the Chinese Academy of Sciences, Professor Gao Mingyuan of Suzhou University and Professor Pang Daiwen of Nankai University are the first scholars to carry out quantum dot research in China. Professor Peng Xiaogang joined Zhejiang University after returning to China in 2009, devoting himself to the research and industrial development of excited state chemical regulation of quantum dots, and inspiring a group of young scholars around him to devote themselves to the research of quantum dots. In 2014, Professor Peng Xiaogang cooperated with Professor Jin Yizheng to report the red QLED electroluminescent device close to the theoretical efficiency in Nature, which was selected as the top ten scientific progress in China in that year [9]. Since then, Chinese scholars have made continuous efforts to improve the performance of QLEDs. For example, Jin Yizheng Research Group and Huang Fei Research Group of South China University of Technology published cooperative work in 2022 to promote the performance of blue and green devices to a level close to industrialization [10]. In addition, Professor Zhong Haizheng of Beijing Institute of Technology and Professor Zeng Haibo of Nanjing University of Science and Technology became the first group of researchers in the world to develop perovskite quantum dots, and they made representative research work on photoluminescence and electroluminescence applications of perovskite quantum dots respectively. More than 100 teachers and 500 students attended the 2nd Symposium on Quantum Dot Chemistry, Physics and Applications held by Zhejiang University

in 2021. China's research on quantum dots covers most of the research directions, and some of the research has formed a parallel and leading trend in the world. At the same time, with the support of the Ministry of Science and Technology, TCL, BOE, Huawei and other enterprises have focused on the layout of quantum dot display technology, and the technological innovation enterprises represented by Hangzhou Nanocrystal and Zhijing Technology have been growing.

(6) Quantum Dots: Continuous Shining Stars

Looking back on the development of quantum dots, it can be said that the award of the Nobel Prize in Chemistry to Professor Bawendi, Professor Brus and Professor Ekimov in 2023 is widely expected. The field of quantum dots opened by them, like bright stars, has been shining in the sky of science for 40 years.

Along the way, it is impossible to go smoothly, and it is bound to be full of twists and turns and doubts. Reflecting on the experience at Bell Labs, Professor Alivisatos said: During the lunch discussion, several senior condensed matter physicists bluntly said that the study of colloidal quantum dots was a waste of time. Semiconductor materials produced from test tubes can never be compared to high-quality samples prepared in high-vacuum chambers " [13].". When Alivisatos, then a postdoc, left lunch, he decided to work harder to prove that he was right to devote himself to quantum dots. Quantum dots in the

dark emit brilliant colors, attracting generations of scientists.

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