CN102509700A - Molecular Beam Epitaxy Growth Method of InAs/GaAsSb Quantum Dots - Google Patents
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- RPQDHPTXJYYUPQ-UHFFFAOYSA-N indium arsenide Chemical class [In]#[As] RPQDHPTXJYYUPQ-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000001451 molecular beam epitaxy Methods 0.000 title claims abstract description 9
- 229910001218 Gallium arsenide Inorganic materials 0.000 claims abstract description 46
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 16
- 239000000956 alloy Substances 0.000 claims abstract description 16
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 12
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 239000000758 substrate Substances 0.000 claims description 31
- 229910000673 Indium arsenide Inorganic materials 0.000 claims description 21
- 239000002096 quantum dot Substances 0.000 claims description 9
- 230000007704 transition Effects 0.000 claims description 9
- 238000000151 deposition Methods 0.000 claims description 8
- 238000002128 reflection high energy electron diffraction Methods 0.000 claims description 7
- 230000009471 action Effects 0.000 claims description 4
- 238000005336 cracking Methods 0.000 claims description 4
- 230000008021 deposition Effects 0.000 claims description 4
- 238000000603 solid-source molecular beam epitaxy Methods 0.000 claims description 4
- 238000001228 spectrum Methods 0.000 claims description 4
- 238000006467 substitution reaction Methods 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 3
- 238000005137 deposition process Methods 0.000 claims description 2
- 238000013101 initial test Methods 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims 1
- 238000002524 electron diffraction data Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 4
- 230000005693 optoelectronics Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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Abstract
本发明公开了属于光电器件制备技术领域的一种InAs/GaAsSb量子点的分子束外延生长方法。具体采用先制备锑含量低GaAsSb合金薄层,然后生长InAs量子点的分子束外延生长工艺制备应力自组装GaAs基InAs/GaAsSb量子点;该方法的生长过程由热力学参数决定,制得的GaAsSb合金受工艺条件影响小,成分容易控制,获得了密度可控的InAs/GaAsSb量子点,为锑化物合金基InAs量子点的在太阳能电池、光电探测器等领域的应用奠定基础。The invention discloses a molecular beam epitaxial growth method of InAs/GaAsSb quantum dots, belonging to the technical field of photoelectric device preparation. Specifically, the stress self-assembled GaAs-based InAs/GaAsSb quantum dots are prepared by the molecular beam epitaxy growth process of first preparing a thin layer of GaAsSb alloy with low antimony content, and then growing InAs quantum dots; the growth process of this method is determined by thermodynamic parameters, and the GaAsSb alloy produced The influence of process conditions is small, the composition is easy to control, and the density-controllable InAs/GaAsSb quantum dots are obtained, which lays the foundation for the application of antimonide alloy-based InAs quantum dots in solar cells, photodetectors and other fields.
Description
技术领域 technical field
本发明属于半导体光电器件制备技术领域,特别涉及应力自组装的一种InAs/GaAsSb量子点的分子束外延生长方法。The invention belongs to the technical field of semiconductor optoelectronic device preparation, in particular to a molecular beam epitaxial growth method of InAs/GaAsSb quantum dots self-assembled by stress.
背景技术 Background technique
应力自组装量子点是最容易与现有光电器件工艺相集成的一类半导体量子点。基于InAs量子点的低阈值激光器已经实现小批量应用,而GaAsSb合金的能级结构可通过组分变化进行较大范围的调节,将InAs量子点与GaAsSb结合起来给能带工程的实施提供了更广阔的空间。Stressed self-assembled quantum dots are a type of semiconductor quantum dots that are most easily integrated with existing optoelectronic device processes. Low-threshold lasers based on InAs quantum dots have been applied in small batches, and the energy level structure of GaAsSb alloys can be adjusted in a wide range through composition changes. wide open space.
目前,人们用锑化物合金设计出众多性能独特的器件结构,但仍有一些因素限制了锑化物器件发展应用,包括锑化物合金生长组分可控性差,在外延生长锑化物时候,偏析严重,锑元素容易积累在外延表面,这对原子在表面的迁移、扩散,以及后续的器件工艺优化都有很大影响。另外,在外延生长GaAsSb合金过程中,As、Sb黏附系数相差较大,同时这项差别受温度影响明显:在较低温度下,合金组分主要由As束流决定,而高温下又主要由Sb束流决定;同时由于MBE生长无法实现温度骤变,尤其是外延片粘In生长时无法获知精确温度,这使得锑化物合金组分的控制成为技术难题。这中间还夹杂着As/Sb互换等问题使得问题变得更加复杂。At present, people use antimonide alloys to design many device structures with unique properties, but there are still some factors that limit the development and application of antimonide devices, including poor controllability of the growth components of antimonide alloys, severe segregation during epitaxial growth of antimonides, Antimony elements are easy to accumulate on the epitaxial surface, which has a great impact on the migration and diffusion of atoms on the surface, as well as subsequent device process optimization. In addition, during the epitaxial growth of GaAsSb alloys, the adhesion coefficients of As and Sb differ greatly, and this difference is significantly affected by temperature: at lower temperatures, the composition of the alloy is mainly determined by the As beam, while at high temperatures it is mainly determined by Sb beam flow is determined; at the same time, because MBE growth cannot achieve sudden temperature changes, especially when epitaxial wafers are grown with In, the precise temperature cannot be known, which makes the control of antimonide alloy components a technical problem. This is also mixed with issues such as As/Sb interchange, which makes the problem more complicated.
本发明在深入研究As/Sb互换过程及InAs量子点自组装生长机理的基础上,提出了一种先制备锑含量低GaAsSb合金薄层,然后生长InAs量子点的分子束外延生长方法。该方法的生长过程由热力学参数决定,制得的GaAsSb合金受工艺条件影响小,成分容易控制,获得了密度可控的InAs/GaAsSb量子点,为锑化物合金基InAs量子点的在太阳能电池、光电探测器等领域的应用奠定基础。On the basis of deeply studying the As/Sb interchange process and the self-assembly growth mechanism of InAs quantum dots, the present invention proposes a molecular beam epitaxy growth method that first prepares a GaAsSb alloy thin layer with low antimony content, and then grows InAs quantum dots. The growth process of this method is determined by thermodynamic parameters. The GaAsSb alloy produced is less affected by the process conditions, and the composition is easy to control. The density-controllable InAs/GaAsSb quantum dots are obtained, which are antimonide alloy-based InAs quantum dots in solar cells, It lays the foundation for the application of photodetectors and other fields.
发明内容 Contents of the invention
本发明的目的是提供一种InAs/GaAsSb量子点的分子束外延生长方法,其特征在于,采用先制备锑含量低GaAsSb合金薄层,然后生长InAs量子点的分子束外延生长工艺制备应力自组装GaAs基InAs/GaAsSb量子点,具体步骤如下:The object of the present invention is to provide a molecular beam epitaxial growth method of InAs/GaAsSb quantum dots, which is characterized in that the stress self-assembly is prepared by the molecular beam epitaxial growth process of first preparing a GaAsSb alloy thin layer with low antimony content, and then growing InAs quantum dots GaAs-based InAs/GaAsSb quantum dots, the specific steps are as follows:
a.GaAs基片脱氧处理:使用固源MBE(分子束外延)设备,As、Sb裂解源束流以As4和Sb4为主,用半绝缘GaAs(100)衬底,进行衬底加热、保温脱氧处理;a. GaAs substrate deoxidation treatment: use solid source MBE (molecular beam epitaxy) equipment, As, Sb cracking source beam current is mainly As 4 and Sb 4 , use semi-insulating GaAs (100) substrate, carry out substrate heating, Insulation deoxidation treatment;
b.GaAs缓冲层的生长:在衬底脱氧完全后,首先生长180-230nm厚的GaAs缓冲层,以减小衬底表面质量对后续生长的影响;b. Growth of GaAs buffer layer: After the substrate is completely deoxidized, a 180-230nm thick GaAs buffer layer is first grown to reduce the influence of substrate surface quality on subsequent growth;
c.GaAsSb外延层的制备:缓冲层生长结束后,关闭Ga源快门,同时保持As保护气氛,使衬底降到工艺中指定的温度,待温度达到后,关闭As快门,并打开Sb阀门和快门,使样品的GaAs表面暴露在Sb束流下20-40秒,在Sb束流作用下,GaAs表面的部分As原子会和Sb发生置换反应,形成GaAsSb薄层;c. Preparation of GaAsSb epitaxial layer: After the growth of the buffer layer is completed, close the Ga source shutter, while maintaining the As protective atmosphere, and lower the substrate to the temperature specified in the process. After the temperature reaches, close the As shutter, and open the Sb valve and The shutter exposes the GaAs surface of the sample to the Sb beam for 20-40 seconds. Under the action of the Sb beam, some As atoms on the GaAs surface will undergo a substitution reaction with Sb to form a GaAsSb thin layer;
d.InAs量子点的生长:关闭Sb快门的同时,恢复As快门,同时升温或者降温到InAs生长温度,温度到后,开始沉积InAs量子点同时密切关注RHEED(反射式高能电子衍射)花样变化,以精确获得临界转变厚度,对于观察形貌的样品,InAs沉积量达临界转变后及时停止生长并降温取出;其中,临界转变厚度在几纳米到几十纳米之间调整;d. Growth of InAs quantum dots: While closing the Sb shutter, restore the As shutter, and at the same time heat up or cool down to the InAs growth temperature. After the temperature is up, start depositing InAs quantum dots and pay close attention to the RHEED (reflection high energy electron diffraction) pattern change. In order to accurately obtain the critical transition thickness, for the sample whose morphology is observed, the InAs deposition amount reaches the critical transition, and the growth is stopped in time and the temperature is lowered to take it out; wherein, the critical transition thickness is adjusted between several nanometers to tens of nanometers;
e.InAs盖层的制备:对于观察光谱的样品,在InAs生长温度下,先沉积3-8nm低温GaAs,而后升温再沉积40-60nm GaAs。e. Preparation of InAs capping layer: For samples to observe the spectrum, at the InAs growth temperature, first deposit 3-8nm low-temperature GaAs, and then heat up and then deposit 40-60nm GaAs.
所述步骤a中GaAs(100)衬底,是通美晶体公司的‘epi-ready’级半绝缘GaAs(100)衬底。The GaAs (100) substrate in the step a is an 'epi-ready' grade semi-insulating GaAs (100) substrate of Tongmei Crystal Company.
所述步骤a中衬底脱氧所用温度均由RHEED观察到脱氧温度重新标定,初试温度为380-420℃,保持30-50分钟。The temperature used for the deoxidation of the substrate in step a is re-calibrated from the observation of the deoxidation temperature by RHEED. The initial test temperature is 380-420° C. and kept for 30-50 minutes.
所述步骤b中GaAs缓冲层生长速率控制在0.6-1.2μm/h,生长温度在570-590℃,V/III比(沉积过程中V族元素和III族元素束源的束流比)在15-25之间。In the step b, the growth rate of the GaAs buffer layer is controlled at 0.6-1.2 μm/h, the growth temperature is at 570-590° C., and the V/III ratio (the beam current ratio of the V group element and the III group element beam source during the deposition process) is at Between 15-25.
所述步骤c中指定的温度为GaAsSb生长温度,在480-500℃之间,Sb速流在1×10-7-2×10-7Torr之间The temperature specified in step c is the GaAsSb growth temperature, between 480-500°C, and the Sb flow rate is between 1×10 -7 -2×10 -7 Torr
所述步骤d中InAs生长温度为480-500℃之间,In速流在1×10-8Torr以下。In the step d, the growth temperature of InAs is between 480-500° C., and the flow rate of In is below 1×10 −8 Torr.
所述步骤e中GaAs盖层生长温度在570-590℃,V/III比在15-25之间。In the step e, the growth temperature of the GaAs cap layer is 570-590° C., and the V/III ratio is between 15-25.
本发明的有益效果是利用分子束外延技术制备密度可控的InAs/GaAsSb量子点,本发明的InAs/GaAsSb量子点体系将基底换成晶格常数更大、禁带宽度更窄的GaAsSb合金,导致不同的量子点生长动力学参数以及新的电学、光学性质。从InAsSb/GaAsSb量子阱角度来看,InAs/GaAsSb量子点是InAsSb润湿层生长停止在初期三维生长刚刚开始的时刻,量子点的电子限制效应比量子阱更强,因此会带来更明显的量子效应。采用不同温度量子点的密度从这为InAs量子点在光电器件方面的实际应用提供了一个新的途径。The beneficial effect of the present invention is to use molecular beam epitaxy to prepare density-controllable InAs/GaAsSb quantum dots. In the InAs/GaAsSb quantum dot system of the present invention, the substrate is replaced by a GaAsSb alloy with a larger lattice constant and a narrower forbidden band width. It leads to different growth kinetic parameters of quantum dots and new electrical and optical properties. From the perspective of InAsSb/GaAsSb quantum wells, InAs/GaAsSb quantum dots stop the growth of the InAsSb wetting layer at the moment when the initial three-dimensional growth begins. The electron confinement effect of quantum dots is stronger than that of quantum wells, so it will bring more obvious Quantum effects. Using the density of quantum dots at different temperatures provides a new way for the practical application of InAs quantum dots in optoelectronic devices.
具体实施方式 Detailed ways
本发明提供一种InAs/GaAsSb量子点的分子束外延生长方法,采用先制备锑含量低GaAsSb合金薄层,然后生长InAs量子点的分子束外延生长工艺制备应力自组装GaAs基InAs/GaAsSb量子点,量子点密度为120/μm2变化到230/μm2。下面结合实施例对本发明进行具体说明:The invention provides a molecular beam epitaxial growth method of InAs/GaAsSb quantum dots. The stress self-assembled GaAs-based InAs/GaAsSb quantum dots are prepared by the molecular beam epitaxial growth process of firstly preparing a GaAsSb alloy thin layer with low antimony content, and then growing InAs quantum dots. , the quantum dot density is changed from 120/μm 2 to 230/μm 2 . The present invention is specifically described below in conjunction with embodiment:
实施例1Example 1
a.GaAs基片脱氧处理:使用固源MBE设备,As、Sb裂解源束流以As4和Sb4为主。用通美晶体公司的‘epi-ready’级半绝缘GaAs(100)衬底,加热到400℃,保持40分钟进行衬底脱氧处理。a. GaAs substrate deoxidation treatment: use solid source MBE equipment, and As and Sb cracking source beams are mainly As 4 and Sb 4 . Use the 'epi-ready' grade semi-insulating GaAs (100) substrate of Tongmei Crystal Company, heat it to 400 ° C, and keep it for 40 minutes for substrate deoxidation treatment.
b.GaAs缓冲层的生长:在衬底脱氧完全后,首先生长200nm厚的GaAs缓冲层以减小衬底表面质量对后续生长的影响;GaAs缓冲层生长速率控制在1μm/h,生长温度在580℃,V/III比为20。b. Growth of GaAs buffer layer: After the substrate is completely deoxidized, a 200nm-thick GaAs buffer layer is first grown to reduce the influence of substrate surface quality on subsequent growth; the growth rate of the GaAs buffer layer is controlled at 1 μm/h, and the growth temperature is at 580°C, V/III ratio is 20.
c.GaAsSb外延层的制备:缓冲层生长结束后,关闭Ga源快门,同时保持As保护气氛,使衬底降到480℃,待温度达到后,关闭As快门,并打开Sb阀门和快门,使样品的GaAs表面暴露在Sb束流下30秒。在Sb束流作用下,GaAs表面的部分As原子会和Sb发生置换反应,形成GaAsSb薄层。c. Preparation of GaAsSb epitaxial layer: After the growth of the buffer layer is completed, close the Ga source shutter, while maintaining the As protective atmosphere, and lower the substrate to 480°C. After the temperature reaches, close the As shutter, and open the Sb valve and shutter, so that The GaAs surface of the sample was exposed to the Sb beam for 30 seconds. Under the action of the Sb beam, some As atoms on the surface of GaAs will undergo a substitution reaction with Sb to form a GaAsSb thin layer.
d.InAs量子点的生长:关闭Sb快门的同时,恢复As快门,同时升温到InAs生长温度480℃。温度到后,开始沉积InAs量子点同时密切关注RHEED花样变化,以精确获得临界转变厚度;对于观察形貌的样品,InAs沉积量达临界转变后及时停止生长并降温取出。d. Growth of InAs quantum dots: While closing the Sb shutter, restore the As shutter, and at the same time raise the temperature to the InAs growth temperature of 480°C. After the temperature is up, start depositing InAs quantum dots and pay close attention to the RHEED pattern changes to accurately obtain the critical transition thickness; for the samples whose morphology is observed, stop the growth in time after the InAs deposition reaches the critical transition and cool down to take it out.
e.InAs盖层的制备:对于观察光谱的样品,在InAs生长温度下,先沉积5nm低温GaAs,而后升温到580℃,以V/III比20,再沉积55nm GaAs;得到的InAs量子点的密度为200/μm2 e. Preparation of InAs capping layer: For samples to observe the spectrum, at the InAs growth temperature, first deposit 5nm low-temperature GaAs, then raise the temperature to 580°C, and then deposit 55nm GaAs with a V/III ratio of 20; the obtained InAs quantum dots The density is 200/μm 2
实施例2Example 2
a.GaAs基片脱氧处理:使用固源MBE设备,As、Sb裂解源束流以As4和Sb4为主,用通美晶体公司的‘epi-ready’级半绝缘GaAs(100)衬底,加热到390℃,保持45分钟进行衬底脱氧处理。a.GaAs substrate deoxidation treatment: use solid source MBE equipment, As, Sb cracking source beam current is mainly As 4 and Sb 4 , use the 'epi-ready' level semi-insulating GaAs (100) substrate of Tongmei Crystal Company , heated to 390°C, and maintained for 45 minutes for substrate deoxidation treatment.
b.GaAs缓冲层的生长:在衬底脱氧完全后,首先生长220nm厚的GaAs缓冲层以减小衬底表面质量对后续生长的影响。GaAs缓冲层生长速率控制在0.8μm/h,生长温度在585℃,V/III比为22。b. Growth of GaAs buffer layer: After the substrate is completely deoxidized, a 220nm thick GaAs buffer layer is first grown to reduce the influence of substrate surface quality on subsequent growth. The growth rate of the GaAs buffer layer was controlled at 0.8 μm/h, the growth temperature was 585°C, and the V/III ratio was 22.
c.GaAsSb外延层的制备:缓冲层生长结束后,关闭Ga源快门,同时保持As保护气氛,使衬底降到500℃。待温度达到后,关闭As快门,并打开Sb阀门和快门,使样品的GaAs表面暴露在Sb束流下30秒。在Sb束流作用下,GaAs表面的部分As原子会和Sb发生置换反应,形成GaAsSb薄层。c. Preparation of GaAsSb epitaxial layer: After the growth of the buffer layer is completed, close the Ga source shutter while maintaining the As protection atmosphere, and lower the substrate to 500°C. After the temperature is reached, the As shutter is closed, and the Sb valve and shutter are opened, so that the GaAs surface of the sample is exposed to the Sb beam for 30 seconds. Under the action of the Sb beam, some As atoms on the surface of GaAs will undergo a substitution reaction with Sb to form a GaAsSb thin layer.
d.InAs量子点的生长:关闭Sb快门的同时,恢复As快门,同时升温到InAs生长温度500℃。温度到后,开始沉积InAs量子点同时密切关注RHEED花样变化,以精确获得临界转变厚度;对于观察形貌的样品,InAs沉积量达临界转变后及时停止生长并降温取出。d. Growth of InAs quantum dots: While closing the Sb shutter, restore the As shutter, and at the same time raise the temperature to the InAs growth temperature of 500°C. After the temperature is up, start depositing InAs quantum dots and pay close attention to the RHEED pattern changes to accurately obtain the critical transition thickness; for the samples whose morphology is observed, stop the growth in time after the InAs deposition reaches the critical transition and cool down to take it out.
e.InAs盖层的制备:对于观察光谱的样品,在InAs生长温度下,先沉积5nm低温GaAs,而后升温到585℃,以V/III比22,再沉积55nm GaAs;得到的InAs量子点的密度为230/μm2。e. Preparation of InAs capping layer: For samples to observe the spectrum, at the InAs growth temperature, first deposit 5nm low-temperature GaAs, then raise the temperature to 585°C, and deposit 55nm GaAs at the V/III ratio of 22; the obtained InAs quantum dots The density is 230/μm 2 .
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CN105514189A (en) * | 2016-01-13 | 2016-04-20 | 中国科学院上海技术物理研究所 | Type-II super-lattice structure based on indium arsenide substrate and preparation method |
CN106409937A (en) * | 2016-04-19 | 2017-02-15 | 中国科学院上海技术物理研究所 | Indium arsenide base II superlattice structure and preparation method |
CN108847385A (en) * | 2018-06-11 | 2018-11-20 | 中国电子科技集团公司第四十四研究所 | A kind of GaAs base InAs quanta point material growth method |
CN110646451A (en) * | 2019-08-27 | 2020-01-03 | 中国电子科技集团公司第十一研究所 | Beam proportion detection method and detection equipment |
CN113358677A (en) * | 2021-06-06 | 2021-09-07 | 南京国科半导体有限公司 | Method for measuring growth speed of InAs layer grown on GaSb substrate |
CN114381801A (en) * | 2021-12-14 | 2022-04-22 | 南京信光半导体科技有限公司 | Molecular beam epitaxy preparation method of high-density and high-uniformity InAs/GaAs quantum dots |
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Cited By (9)
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CN105514189A (en) * | 2016-01-13 | 2016-04-20 | 中国科学院上海技术物理研究所 | Type-II super-lattice structure based on indium arsenide substrate and preparation method |
CN106409937A (en) * | 2016-04-19 | 2017-02-15 | 中国科学院上海技术物理研究所 | Indium arsenide base II superlattice structure and preparation method |
CN108847385A (en) * | 2018-06-11 | 2018-11-20 | 中国电子科技集团公司第四十四研究所 | A kind of GaAs base InAs quanta point material growth method |
CN108847385B (en) * | 2018-06-11 | 2020-11-06 | 中国电子科技集团公司第四十四研究所 | GaAs-based InAs quantum dot material growth method |
CN110646451A (en) * | 2019-08-27 | 2020-01-03 | 中国电子科技集团公司第十一研究所 | Beam proportion detection method and detection equipment |
CN110646451B (en) * | 2019-08-27 | 2022-08-19 | 中国电子科技集团公司第十一研究所 | Beam proportion detection method and detection equipment |
CN113358677A (en) * | 2021-06-06 | 2021-09-07 | 南京国科半导体有限公司 | Method for measuring growth speed of InAs layer grown on GaSb substrate |
CN114381801A (en) * | 2021-12-14 | 2022-04-22 | 南京信光半导体科技有限公司 | Molecular beam epitaxy preparation method of high-density and high-uniformity InAs/GaAs quantum dots |
CN114381801B (en) * | 2021-12-14 | 2024-07-23 | 南京信光半导体科技有限公司 | Molecular beam epitaxy preparation method of high-density high-uniformity InAs/GaAs quantum dots |
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