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  1. (Professor, Physico-Technical Institute of the Academy of Sciences of the Republic of Uzbekistan E-mail: amin@uzsci.net, shukrullousmonov66@gmail.com, dada@uzsci.net,eshonxojayevdilmurod34@gmail.com)
  2. (Professor, Urgench State University, Urgench, Uzbekistan E-mail: umida72@rambler.ru)
  3. (Kumoh National Institute of Technology, Gumi-si, Gyeongsangbuk-do, South KoreaE-mail: w.suxrob.w@gmail.com)



solid solution, molecular substitution, epitaxial layer, heterostructure, spectral photosensitivity, nanocrystallites, near-ir regions of the radiation spectrum.

1. Introduction

Growing semiconductor solid solutions is of undoubted interest for the development of modern semiconductor instrumentation, since a solid solution synthesized from several semiconductor components can combine the advantages of each of them. The works [1-4] show that by preparing solid solutions with many components, it is possible to achieve the desired molecular bond and symmetry of crystals, as well as accurately control the cell size and obtain many other physicochemical properties. Solid solutions are constantly being studied with the aim of rationally modifying structures and understanding the principles of crystal packing.

When elemental semiconductors or semiconductor compounds do not meet the technical requirements for a particular device, a new solid solution is synthesized from several semiconductors that meets the requirements. It should be noted that, by smoothly varying the composition of the solid solution, one can control the main electrophysical and optical parameters of the material [5- 8], such as the band gap, spectral photosensitivity region, lattice parameter, etc.

The paper [7] reviews solid solution strategies used in molecular conductors, where the main goal is to control their transport and magnetic properties (metallic or superconducting behavior, metal-insulator transitions, etc.).The main features of molecular conductors are described to determine which molecular compounds are prone to being replaced by others in solid solutions, to what extent and for what purpose.

In order to obtain a high-quality solid solution suitable for creating devices, the closeness of the lattice parameters of the solid solution components is of great importance.

The crystal structure of InSb has a cubic syngony of the zinc blende type, with a crystal lattice constant of 0.648 nm. Gray tin Sn also forms cubic crystals, with a crystal lattice constant of 0.646 nm, with a diamond–like structure. Therefore, they are promising pairs that form substitutional solid solutions of the (InSb)1–z(Sn2)z type [9].

In this regard, the solid solution consisting of the components GaAs, ZnSe and InSb of undoubted interest, since the sum of the covalent radii of the atoms of the molecules of these semiconductors is very close [9, 10], and the band gaps in them (Eg) differ significantly (Eg, GaAs = 1.43 eV, Eg, ZnSe = 2.68 eV and Eg, Ge = 0.67 eV) [11].

There is every reason to believe that a solid solution consisting of these components will have a qualitative crystallographic structure, and the spectral sensitivity region will cover the fundamental agreement regions of germanium, gallium arsenide, and zinc selenide. The expansion of the region of spectral photosensitivity is of great importance for the creation of efficient photovoltaic devices, including photodetectors and solar cells. In this work, we studied the possibility of forming a solid solution of molecular substitution based on GaAs, Ge, and ZnSe and identified the optimal technological conditions for growing single-crystal epitaxial layers of a solid solution of molecular substitution (GaAs)1-y-z(Ge2)y(ZnSe)z on GaAs substrates, as well as the atomic- force microscopy of the epitaxial film surface and the spectral dependence of the n-GaAs–n+(GaAs)1-x-y(Ge2)x(ZnSe)y heterostructure.

2. Materials and methods

The possibility of the formation of a solid solution of molecular substitution between the GaAs, Ge, and ZnSe components was estimated based on the criteria given in formulas (1) and (2) [11].

(1)
$∆ z =\left(z_{III}+ z_{V}\right)-\left(z_{IV}+ z_{IV}\right)=0 \\ ∆ z =\left(z_{II}+ z_{VI}\right)-\left(z_{IV}+ z_{IV}\right)=0 \\ ∆ z =\left(z_{III}+ z_{V}\right)-\left(z_{II}+ z_{VI}\right)=0$
(2)
$∆r=\left(r_{III}+ r_{V}\right)-\left(r_{IV}+ r_{IV}\right) 0.1∙\left(r_{III}+ r_{V}\right) \\ ∆r=\left(r_{III}+ r_{V}\right)-\left(r_{IV}+ r_{IV}\right) 0.1∙\left(r_{IV}+ r_{IV}\right) \\ ∆r=\left(r_{III}+ r_{V}\right)-\left(r_{II}+ r_{VI}\right) 0.1∙\left(r_{III}+ r_{V}\right)$

where zII, zIII, zIV, zV, zVI are the valences of atoms of groups II, III, IV, V, and VI, rII, rIII, rIV, rV, rVI and rVI are the covalent radii of atoms of groups II, III, IV, V, and VI, respectively.

According to these criteria, the valency of the mutually substituting components should be the same (1) and the difference in the covalent radii of the molecules should not exceed 10%. Since the sum of the covalent radii of the atoms of the GaAs, Ge, and ZnSe semiconductor molecules is very close (rGa + rAs = 2.44 Å, rZn + rSe = 2.45 Å and rGe + rGe = 2.44 Å), and the sum of the valences of the atoms of the molecules are the same and equal to 8, the criteria substitution solid solution formations (1) and (2) are performed. Therefore, it can be said that the GaAs, Ge, and ZnSe components can form a substitutional solid solution with a good crystallographic structure.

The temperature of decomposition (formation) of the IV–IV, III–V, II–VI, I–VII, and other compounds becomes a decisive factor for the formation of solid solutions of these compounds. The temperature interval of the existence of the IV IV, III–V, II–VI, I–VII, and new compounds is determined from the condition.

EIV–VI ,EIII–V ,EII–VI, EI–VII > γ/N,

where EIV–VI ,EIII–V ,EII–VI, EI–VII are the energies of bonding between atoms of the IV–IV, III–V, II–VI, and I–VII molecules, respectively; and N is the num ber of atoms in the solid solution.

For the Ge–GaAs system considered as an example, we can expect that, at temperatures close to the eutectic temperature (~860°C) and above, the Ge2 and GaAs molecules are most likely unstable; consequently, the phase diagram of this system does not contain regions of solid solu tions. The epitaxial growth of (Ge2)x(GaAs)1–x layers usually proceeds at temperatures where the Ge2 and GaAs molecules are stable, and the solid solution of the Ge2 and GaAs compounds is formed [12–15].

To grow such a solid solution between GaAs, Ge, and ZnSe, it is necessary to create thermodynamic conditions, which were achieved on the basis of the liquid phase model with molecular components proposed by A.S. Saidov. According to this model, semiconductor compounds of the АIIIВVI and АIIВVI classes, as well as elementary semiconductors such as Ge and Si, when dissolved in liquid metals (Ga, Sn, In. Bi. Pb, etc.) at temperatures much lower than the melting point of the corresponding substances , are mainly in the form of molecules (Fig 1). The solubility of binary compounds GaAs and ZnSe, as well as atomic substances Ga, As, Zn, and Se, in Bi was studied at various temperatures.

Fig. 1. Dissolved molecules GaAs, ZnSe and Ge2 in Bi at 750° C.

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The validity of this model for the selected Bi-GaAs-ZnSe system is confirmed by the fact that the binary compounds GaAs and ZnSe in Bi have a very low solubility. While their individual components, i.e. atomic substances Ga, As, Zn and Se, at the same temperatures, have unlimited or very high solubility in Bi (Fig.3, 4). This shows that the GaAs and ZnSe binary compounds dissolved in Bi at a temperature of 750°S do not decompose into individual Ga and As atoms, as well as Zn and Se, but are in the form of GaAs and ZnSe molecules.

Fig. 2. Dissolution of gallium arsenide in the form of GaAs molecules (a), as well as gallium and arsenic in the form of individual Ga and As atoms (b) in Bi at a temperature of 750°C.

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Fig. 3. Dissolution of zinc selenide in the form of ZnSe molecules (a), as well as zinc and selenium in the form of individual Zn and Se atoms (b) in Bi at a temperature of 750°C [12–15].

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3. Results and discussion

Epitaxial layers of the (GaAs)1-у-z(Ge2)y(ZnSe)z solid solution were grown on n-type GaAs (111) substrates. The melt solution bounded between two horizontally arranged substrates consisted of Bi, GaAs, Ge, and ZnSe. The thickness of the gap between the substrates was varied in the range from 0.45 to 1.6 mm using special graphite props. Growing temperature 750°S. The film thickness was 10–15 µm. The type of conductivity, concentration, and mobility of carriers in the obtained epitaxial films of solid solutions (GaAs)1-у-z(Ge2)y(ZnSe)z were measured on an ECOPIA setup (Hall Effect Measurement system HMS-550+AHT55T5). The resulting epitaxial films had n-type conductivity. The carrier concentration and mobility were ~ 5∙1020 sm-3 and µ - 9.2-11 sm2/(Vs), respectively.

On Fig 4 shows the crystal lattice of a solid solution of molecular substitution (GaAs)1-y-z(Ge2)y(ZnSe)z. As can be seen from Fig 4, in the crystal lattice of the solid solution there are covalent bonds such as Ga-As, Ga-Ge, Ga-Se, Zn-Se, Zn-As, Zn-Ge, Ge-Ge, Ge-As, Ge-Se. Since the breaking energies of such covalent bonds are different, they can contribute to the appearance of the corresponding peaks in the photosensitivity spectrum of the solid solution.

Fig. 4. Hypothetical crystal lattice of the solid solution (GaAs)1-у-z(Ge2)y(ZnSe)z

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The surface of the resulting epitaxial films was examined using an SPM 9700HT (Shimadzu) atomic force scanning microscope. When examining the surface of the films, nanocrystallites were detected (Fig 5) with a height of 6.5-7.5 nm. The width at the base of the nanocrystallites was ~120–150 nm (Fig 6). The concentration of nanocrystallites (quantum dots) on the surface of the epitaxial film was 2.5∙108 sm-2.

Spectral photosensitivity of n-GaAs–n+-(GaAs)1-y-z(Ge2)y(ZnSe)z structures

On Fig 7 shows the dependence of the photosensitivity of the n-GaAs–n+-(GaAs)1-y-z(Ge2)y(ZnSe)z heterostructure on the photon energy (Eph). It can be seen that the spectral photosensitivity of the studied structure has a complex character and covers a wide range of photon energies, from 1.3 to 2.5 eV. In the photon energy range of 1.5–2.4 eV, the sensitivity is not monotonic; there are subtle rises at Eph = 1.5 eV and 1.9 eV. This is apparently due to the inhomogeneity of the composition of the solid solution.

Fig. 5. Three-dimensional image of the surface of the epitaxial film (GaAs)1-x-y (Ge2)x(ZnSe)y, obtained using an atomic force microscope, Image size 5x5 μm2

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The molar ratios of the components GaAs (Eg, GaAs = 1.43 eV), Ge (Eg, Ge = 0.67 eV), and ZnSe (Eg, ZnSe = 2.68 eV) are different over the thickness of the epitaxial film; accordingly, each sublayer of the solid solution has its own fundamental absorption region.

Fig. 6. Dimensions of quantum dots on the surface of the solid solution

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(GaAs)1-x-y(Ge2)x(ZnSe)y: width - 120-150 nm, height - 6.5-7.5 nm, the distance between quantum dots is 300-450 nm. In our case, it is determined by the thickness of the n+-(GaAs)1-y-z (Ge2)y(ZnSe)z epitaxial layer and is ~10 µm. When the diffusion length of charge carriers is less than the thickness of the separating barrier, then the electron-hole pairs generated by high-energy photons in the near-surface region of the structure do not reach the separating barrier and do not participate in the creation of a photocurrent. Therefore, the sensitivity of the structure in the short-wavelength region of the radiation spectrum decreases.

Fig. 7. Spectral dependences of the photosensitivity of the n-GaAs-n+(GaAs)1-x-y (Ge2)x(ZnSe)y structure at 300 K.

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4. Conclusion

The physico-technological features of growing a new solid solution of molecular substitution (GaAs)1-y-z(Ge2)y(ZnSe)z on GaAs (111) substrates from a limited volume of Bi solution-melt are studied. The optimal thermodynamic conditions for growing single-crystal epitaxial films of the (GaAs)1-y-z(Ge2)y(ZnSe)z solid solution are determined. The spectral dependence of the photosensitivity of the n-GaAs-n+(GaAs)1-x-y(Ge2)x(ZnSe)y structure covers the photon energy range from 1.3 eV to 2.5 eV, with maxima at 1.6 eV, 2.0 eV and 2.4 eV. It has been found that the (GaAs)1-y-z (Ge2)y(ZnSe)z solid solution has selective photosensitivity due to the peculiarities of Ge and ZnSe nanocrystals in the epitaxial layer, with different ionization energies of the corresponding molecules. Studying the patterns of formation of an ordered set of nanosized crystals in the bulk or on the surface of a (GaAs)1-y-z (Ge2)y(ZnSe)z solid solution makes it possible to control the sizes of nanocrystals, manufacture devices operating on the basis of the size effect, and expand the range of spectral sensitivity of this material. Solid solutions (GaAs)1-y-z(Ge2)y(ZnSe)z can be used as a photoactive material for a selective photodetector operating in the near-IR and visible regions of the radiation spectrum.

Acknowledgements

Hello dear editorial members of The Transactions of the Korean Institute of Electrical Engineers (KIEE)! Thank you for taking the time to review our article on Investigation of the Spectral Photosensitivity of nGaAs-n+(GaAs)1-x-y(Ge2)x(ZnSe)y Heterostructure Obtained from Bi Solution-Melt! We would also like to thank the reviewers who have reviewed our article. We are pleased that the reviewers of the article, in turn, gave a fair and accurate assessment. We hope to co-publish more scientific articles with your journal in the future. We also wish the members of the magazine's editorial board and the magazine's activities good luck! In the future, we wish to increase the ranking of the magazine in the Scopus database, and in this regard, we, as the author, will promote your magazine and the published scientific articles more widely among the scientists of Uzbekistan.

Sincerely, the author, Shavkat Ismailov!

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저자소개

Ismailov Shavkat Kuzievich
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In 1990 he graduated from the Faculty of Physics of the National University of Uzbekistan with the specialty Theoretical Physics. Since 1990, he worked at the Physico-Technical Institute of the Academy of Sciences of Uzbekistan, and since 1992 at Urgench State University. In 2007, he defended his dissertation on the topic “Growth and research of electronic and optical properties of semiconductor solid solutions” and received a Doctor of Science degree in the specialty “Physics of Semiconductors and Dielectrics”. Until 2016, he worked as an associate professor at the Department of Physics at Urgench State University. Since 2016, he has been the head of the Department of Telecommunication Engineering at the Urgench branch of Tashkent University of Information Technologies. Under the project ERASMUS- EDU-2022-101083224 within the framework of the ERASMUS+ program of the European Union, he completed an internship at the Belgian universities of Gent and VRIJE of Brussels (VUB), and the Polytechnic University of Turin (Politeknico di Torino).

He is the author or co-author of more than 60 peer-reviewed journal and conference articles, 2 monographs and 3 textbooks, and 6 scientific articles indexed in the Scopus (Elsevier) database. He can be contacted at ishavkat6819@gmail.com

Saidov Amin Safarbaevich
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In 1984 he received the degree of Doctor of Physical and Mathematical Sciences. He is a professor at the laboratory “Growth of Semiconductor Crystals” at the Physico-Technical Institute of the Academy of Sciences of the Republic of Uzbekistan. Laureate of the State Prize of the Republic of Uzbekistan "On awarding state prizes of the Republic of Uzbekistan in 2007 in the field of science and technology, literature, art, and architecture" for internationally recognized fundamental research "New semiconductor solid solutions and impurity effects of semiconductors".He created a scientific direction on the physicochemical basis of the synthesis technology for new semiconductor solid solutions IV1-xIVx, (IV2)1-x(A3B5)x, (IV2)1-x(A2B6)x, (IV2)1-x-y(A3B5)x (A2B6)y on silicon substrates, and their homo- and heterostructures. For the first time he detected impurity photovoltaic, thermal-voltaic, phototemplotvoltaic effects, as well as the effect of two-color radiation in a single crystal. Polycrystalline silicon with a purity of 99.9 atomic% was obtained by an ecologically clean method in a small solar furnace by repeated remelting of metallurgical silicon in the open air.Scientific interests: interaction of impurities in diamond-like semiconductors and physical bases for growing silicon, gallium arsenide, aluminum-gallium arsenide, high-resistance, homogeneous and graded band gap, new solid solutions IV1-xIVx, (IV2)1-x(A3B5)x, (IV2)1-x (A2B6)x, (IV2)1-x-y(A3B5)x (A2B6)y on silicon substrates, as well as homo- and heterostructures based on them. Published 2 monographs, 1 collection of articles, more than 277 scientific articles and 36 patents. He can be contacted at amin @uzsci.net

Usmonov Shukrullo Negmatovich
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In 1989 he graduated from the Faculty of Physics of St. Petersburg State University with a degree in Radiophysics. In 1994, he graduated from doctoral studies at the Physico-Technical Institute of the Academy of Sciences of Uzbekistan with a specialty in “Physics of Semiconductors and Dielectrics” and received the degree of Candidate of Physical and Mathematical Sciences (PhD); in 2018, he received the degree of Doctor of Physical and Mathematical Sciences (DSc) with a degree in Semiconductor Physics. In 2009, with a degree in Semiconductor Physics, he received a diploma of “Senior Researcher” from the Academy of Sciences of Uzbekistan. Currently he is the head of the laboratory “Growth of Semiconductor Crystals” at the Physico-Technical Institute of the Academy of Sciences of Uzbekistan. Under his leadership, 2 candidates of science (PhD) were trained. His research interests include photoelectric, thermovoltaic and luminescent effects in semiconductor materials, the interaction and distribution of chemical elements and compounds in multicomponent single- and two-phase systems in relation to the current needs of semiconductor materials science and solid- state electronics, as well as the technology of epitaxial films of two and multicomponent semiconductor solid solutions elementary semiconductors and binary compounds III-V and II-VI. He is a member of the editorial board of the international scientific journal Applied Solar Energy, author or co-author of more than 230 articles published in peer- reviewed scientific journals and scientific conference proceedings, 1 patent for an invention, 1 monograph, 3 study guides and 2 textbooks, including 50 indexed scientific articles in the Scopus database (Elsevier). He can be contacted at shukrullousmonov66@gmail.com.

Saparov Dadajan Valixanovich
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He graduated from the Tashkent State Pedagogical Institute named after Nizami in1983. From 1986 to present, he has been working in the Physical-Technical Institute of the Academy of Sciences of the Republic of Uzbekistan. In 2020, he received his PhD on the growth of epitaxial GaSb and GaP films on Si substrates from the liquid phase. Currently, he is a senior researcher at the laboratory “Growth of Semiconductor Crystals” at the Physical- Technical Institute of the Academy of Sciences of the Republic of Uzbekistan and is engaged in growing epitaxial films of various semiconductor solid solutions on silicon substrates from a melt solution. He can be contacted at dada@uzsci.net

Eshonkhojaev Dilmurod Odilovich
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In 1987-1992, he graduated from Tashkent State Technical University, majoring in "engineer- mechanics in the field of aircraft construction. In 1993-1994 he worked as an engineer designer at the Andijonmash plant. In 1994-1997 he was the chief customs committee of the State Tax Committee, Andijan region worked as an inspector in the customs service, and in 1999-2012, he worked as the head of the department for spiritual and educational affairs in the scientific and educational center in the form of a limited liability company for youth development in Andijan. In 2012-2014, he worked as a leading specialist in the executive committee of the Andijan regional council of the National Democratic Party of Uzbekistan. From 2014 to now, he has been an assistant at the Andijan Institute of Mechanical Engineering. He can be contacted at eshonxojayevdilmurod 34@gmail.com

Asatova Umida Palvanovna
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In 1994 she graduated from the Faculty of Physics of Tashkent State University. That same year, he joined Urgench State University as a research intern. From 1995 to 2001 she worked as a teacher at the Department of Physics at Urgench State University, and from 2001 to 2017 as a senior teacher. In 2017- 2020 he studied at Urgench State University in the direction of “04/01/10-Physics of Semiconductors” in doctoral studies. On May 22, 2021, at a meeting of the Academic Council under number DSс.03/30.12.2019.FM/T.01.12 at the Research Institute of Semiconductor Physics and Microelectronics of the National University of Uzbekistan on the topic “Narrow- gap solid solutions Gе1- xSnх, (InSb)1-x (Sn2)x and their photoelectric properties” defended her dissertation and received a PhD in physics and mathematics. From 2021 to the present, he has been working as an associate professor at the Department of Physics at Urgench State University. Umida Asatova is the author of about 40 scientific works, including 15 articles in scientific journals, 25 theses at international and republican scientific and practical conferences. In 2022 she published a monograph on the topic “Physics and technology for producing solid solutions of narrow-gap semiconductors” and in 2023 a textbook “Contact phenomena in semiconductors”.

Umida Asatova worked from January 03, 2018 to December 31, 2018 in the state grant project No. ОТ-Ф2-65 on the topic “Study of the laws of scattering of low-energy ions on the surface of semiconductor single crystals of type AIIIBV,” and from January 05, 2022 to 31 December 2022 in the project of the state grant UZB-Ind-2021-88 on the topic “Research of hydrophobic and superhydrophobic materials using nanostructures.” Umida Asatova is a participant in the scientific seminar PhD.03/30.09.2020.FM.55.04 in the specialty “01.04.04 – Physical Electronics”, opened at Urgench State University and works as the secretary of the scientific seminar PhD.03/29.12.2022.FM.55.07 on specialty “04/ 01/11 – Laser physics”She can be contacted at umida72@rambler.ru

Bobojanov Sukhrob Gayratovich
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received his BS degree in Telecommunication Engineering from the Urgench branch of Tashkent University of Information Technologies, Uzbekistan, in 2015. He received his MS degree in Telecommunication Technologies from Tashkent University of Information Technologies named after Muhammad al-Khwarizmi, Uzbekistan, in 2017. From 2017 to 2018, he worked as an engineer in the Department of Technical Coordination and Support of State Events at Urgench Branch of "Uzbektelecom" JSC. From 2018 to 2020, he worked as an assistant teacher in the Department of Telecommunication Engineering at Urgench Branch of Tashkent University of Information Technologies named after Muhammad al-Khwarizmi in Urgench, Uzbekistan. He received his Ph.D. degree in Software Engineering from Kumoh National Institute of Technology, Gumi, South Korea in 2024. He can be contacted at w.suxrob.w@ gmail.com.