WO2013020423A1 - 一种量子点材料的制作装置及制作方法 - Google Patents

一种量子点材料的制作装置及制作方法 Download PDF

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WO2013020423A1
WO2013020423A1 PCT/CN2012/078013 CN2012078013W WO2013020423A1 WO 2013020423 A1 WO2013020423 A1 WO 2013020423A1 CN 2012078013 W CN2012078013 W CN 2012078013W WO 2013020423 A1 WO2013020423 A1 WO 2013020423A1
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quantum dot
temperature
epitaxial layer
interference image
growth chamber
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PCT/CN2012/078013
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English (en)
French (fr)
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彭长四
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苏州大学
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Priority to US14/233,679 priority Critical patent/US8969185B2/en
Priority to EP12821709.8A priority patent/EP2741315B1/en
Publication of WO2013020423A1 publication Critical patent/WO2013020423A1/zh

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02587—Structure
    • H01L21/0259—Microstructure
    • H01L21/02601—Nanoparticles
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02538—Group 13/15 materials
    • H01L21/02546—Arsenides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02367—Substrates
    • H01L21/0237—Materials
    • H01L21/02387—Group 13/15 materials
    • H01L21/02395—Arsenides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02587—Structure
    • H01L21/0259—Microstructure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02612—Formation types
    • H01L21/02617—Deposition types
    • H01L21/02631—Physical deposition at reduced pressure, e.g. MBE, sputtering, evaporation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02656—Special treatments
    • H01L21/02664—Aftertreatments
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
    • H01S2304/00—Special growth methods for semiconductor lasers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
    • H01S2304/00—Special growth methods for semiconductor lasers
    • H01S2304/02—MBE
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
    • H01S2304/00—Special growth methods for semiconductor lasers
    • H01S2304/04—MOCVD or MOVPE
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
    • H01S5/00—Semiconductor lasers
    • H01S5/30—Structure or shape of the active region; Materials used for the active region
    • H01S5/34—Structure or shape of the active region; Materials used for the active region comprising quantum well or superlattice structures, e.g. single quantum well [SQW] lasers, multiple quantum well [MQW] lasers or graded index separate confinement heterostructure [GRINSCH] lasers
    • H01S5/341—Structures having reduced dimensionality, e.g. quantum wires
    • H01S5/3412—Structures having reduced dimensionality, e.g. quantum wires quantum box or quantum dash

Definitions

  • the invention relates to the technical field of manufacturing low-dimensional semiconductor materials, and in particular to a device and a manufacturing method for a quantum dot semiconductor material.
  • Quantum dot low-dimensional nanostructured materials exhibit excellent photoelectric properties due to their unique electronic structure and density of states. They have broad application prospects in the fields of nanoelectronics, optoelectronics, life sciences and quantum computing.
  • Theoretical analysis shows that quantum dot lasers have superior performance in many respects than quantum well lasers. Such as higher gain, lower threshold current, higher quantum efficiency and better thermal stability.
  • quantum dot electrons By using the "puncturing" effect of quantum dot electrons, it is possible to precisely control the number of electrons entering or leaving the quantum dot to a single electron precision, thereby making a single electron transistor. Quantum dots are also expected to be applied to solid-state quantum computing, vertical incident photodetectors, and the like.
  • the self-organized growth of s- ⁇ mode is the most widely studied method for the preparation of quantum dot materials with important application value.
  • the main principles are as follows: In the epitaxial growth process of molecular beam epitaxy (MBE), the semiconductor material with different lattice constants is different from the substrate plane in the growth direction. stress. Stress build-up to a certain extent releases these stresses by surface atom migration and aggregation, or by the creation of misfit dislocations. The former aggregated into a heap of atoms will grow up during the growth process and be buried in the subsequently grown epitaxial material to form quantum dots.
  • the initial atomic group formed by the need for stress release is the "seed" of quantum dot growth, and the subsequent quantum dots are formed by the growth of these "seeds".
  • quantum dots are quantum dots of "disordered" self-organized growth (dynamic random growth) grown in the SK mode epitaxial growth mode of Fig. 1A.
  • the advantage is that it is defect-free, can be used for the fabrication of actual devices, and has proven to be significantly superior to other materials in its class.
  • the quantum dots thus grown cannot be used to fabricate quantum information devices, and even if a small number of devices that can be operated from a large number of devices prepared by a large-scale device process are found to have a small number of working devices, the performance of each device may vary greatly. This "disordered" quantum dot is also difficult to prepare a relatively high power laser because the gain spectrum is too wide.
  • Fig. 1B are obtained by ejecting etching gas to the bottom of the village in situ, etching some micropores on the surface of the substrate, and then growing quantum dot twins at the positions of the micropores, and "Disordered" self-organized quantum dots have a certain order, but there are many etching defects in the micropores etched by the etching gas, and these defects are retained in the process of growing quantum dots. Even zoom in.
  • the "long-range order" quantum dots in Fig. 1C are obtained by previously etching the nano pattern template by conventional nanofabrication technology, and then epitaxially growing quantum dots on the template.
  • defects introduced by conventional nanostructures are larger than the defects caused by the etching of micropores by etching gas, both in size and scale. Defects in the "short-range order" and “long-range order” quantum dots make the devices they make inoperable.
  • the present invention provides an apparatus and method for fabricating a quantum dot material, which can control the growth position of a quantum dot in an epitaxial process, and can not only produce a long-range ordered quantum dot material, but also because There is no need to perform any etching treatment on the bottom of the village, so it does not cause defects caused by etching.
  • a quantum dot fabrication apparatus comprises an epitaxial device and an optical device for generating an interference image
  • the epitaxial device comprising a growth chamber, the growth chamber being a vacuum chamber for placing a village bottom Material, the growth chamber wall is provided with a plurality of light rays for injection a window
  • the optical device includes a laser light source and a modulated light path, and after the light beam is emitted from the laser light source, the modulated light path is divided into a plurality of beams, and the plurality of light beams respectively pass through the plurality of windows and then enter the growth chamber, and The surface of the substrate material forms an interference image.
  • the plurality of windows are three, and each of them is equally spaced around the cavity wall of the growth chamber.
  • the modulated light path is divided into three beams, and the three beams are respectively incident into the growth chamber through the three windows, and a three-beam interference image is formed on the surface of the substrate material.
  • the plurality of windows are four, and each of them is equally spaced around the cavity wall of the growth chamber.
  • the modulated light path is divided into four beams, and the four beams are respectively incident into the growth chamber through the four windows, and a four-beam interference image is formed on the surface of the substrate material.
  • the laser light source is a pulsed laser light source.
  • a method for fabricating a quantum dot material simultaneously proposed according to the object of the present invention is produced by using the above quantum dot material manufacturing apparatus, comprising the steps of:
  • the interference image is removed, the epitaxial layer continues to be deposited, and finally quantum dots are formed on the surface of the epitaxial layer.
  • the interference image is a periodic lattice, and in the interference enhancement region of the periodic lattice, the temperature of the epitaxial layer is raised to a second temperature.
  • an interference image is applied to the epitaxial layer.
  • a regularly distributed temperature field is formed on the epitaxial layer, so that the epitaxial layer begins to form an atomic aggregation phenomenon at a higher temperature point, and no atomic aggregation occurs in a relatively low temperature region.
  • the position of the quantum dot can be artificially controlled, and a long-range ordered quantum dot fabrication method can be realized.
  • Figure 1 A - 1 C are the quantum dot distribution maps on the existing quantum dot materials
  • 2 is a temperature distribution diagram of an interference image generated by three-beam interference
  • FIG. 3 is a view showing an apparatus for fabricating a quantum dot material according to a first embodiment of the present invention
  • FIG. 4 is a view showing a device for fabricating a quantum dot material according to a second embodiment of the present invention.
  • Figure 5 is a flow chart of a method for fabricating a quantum dot material of the present invention.
  • quantum dots formed by the SK mode self-organized growth mode are used, The long process is random, so the distribution of quantum dots obtained in this way is unordered.
  • quantum dots grown by making regular patterns on the surface of the substrate have a long range of order within a certain range, but in the preparation process, the matrix is easily damaged and a large number of crystal defects are generated, which greatly affects the photoelectricity of the quantum dots. characteristic.
  • the present invention proposes a method of fabricating a quantum dot material.
  • the fabrication method utilizes a regularly distributed temperature field on the surface of the film layer while epitaxially growing the film layer, so that the effect of generating a higher concentration of the surface temperature of the film layer is faster than that of other regions having a lower temperature.
  • the "seeds" of quantum dots form a regular distribution under the guidance of the temperature field, thereby producing long-range ordered quantum dot materials.
  • MBE quantum dot molecular beam epitaxy
  • the epitaxial growth of InAs layer in GaAs is an example, and the criticality at low temperature (below 430 °C).
  • the thickness is more than 2.5 times the critical thickness at high temperatures (above 460 °C). That is to say, at different temperatures, the thickness of the film required to produce an atomic aggregation effect is different.
  • the critical thickness required in low temperature environments is often larger than that in high temperature environments, and the low temperature and high temperature are only a relative concept. It is possible to use tens of degrees to several hundred degrees between the two.
  • the epitaxial layer can be grown on the substrate, a regular distribution of temperature is formed on the surface of the epitaxial layer, so that the temperature of the partial region reaches a relatively high temperature required to form the first critical thickness, and other partial regions The temperature only reaches the relatively low temperature required to form the second critical thickness. It can be foreseen that when the thickness of the epitaxial layer reaches the first critical thickness and is less than the second critical thickness, atomic agglomeration has begun in the relatively high temperature region, and other regions at relatively lower temperatures are insufficient for The atoms begin to gather. In this way, through the temperature change The ability to artificially guide the generation of quantum dots, so that quantum dots produce a regular long-range order distribution.
  • the key to the invention is how to provide a regularly distributed temperature field on the epitaxial layer.
  • Direct writing laser interference lithography (DW-LIL) technology is maskless, directly writeable, high efficiency (right), pattern (computer) program-controlled conversion, non-staining, non-contact, large innovative technologies with low area, low cost and low environmental requirements.
  • the basic principle of laser interference lithography is to use two or more coherent lasers to superimpose on the surface of the sample to produce an interference pattern.
  • the electric field in the superimposed region is the vector sum of the electric fields of the respective coherent beams, and the different electric field distributions correspond to different interference patterns.
  • the interference image caused by the interference of the two beams is a bar-shaped image of light and dark
  • the interference image caused by the interference of the three beams or the interference of the four beams is a periodic lattice of a hexagonal or tetragonal shape.
  • direct-write laser interference lithography utilizes the optical properties of the interferometric image to cause the photosensitive material to mutate in areas where the interference enhancement zone is bright or bright, thereby forming an etched pattern on the surface of the material.
  • the temperature distribution of the interference image is extremely important.
  • Fig. 2 is a temperature distribution diagram of an interference image generated by four-beam interference. As shown in the figure, the temperature difference between the region with the highest temperature and the region with the lowest temperature exceeds 1000 °C.
  • FIG. 3 is an apparatus for fabricating a quantum dot material according to a first embodiment of the present invention.
  • the quantum dot fabrication apparatus 10 of the present invention includes an epitaxial device 110 and an optical device 120 for generating an interference image.
  • the epitaxial device 110 includes a growth chamber 101, which is a vacuum chamber in which the substrate material 200 is placed.
  • the chamber of the growth chamber 101 is provided with a plurality of windows 111 for allowing light to enter, since in the present embodiment, three are used.
  • the light beam interferes, so there are three windows 111 here, and each of them is equally spaced around the cavity wall of the growth chamber 101, so that the three beams of light pass through the three windows 111 respectively, and are gathered together at intervals of 120 degrees.
  • a three-beam interference image is formed.
  • Optical device 120 includes a laser source 121 and an optical path 122.
  • Various optical components for adjusting and modulating the optical path are provided in the optical path 122, such as a collimator lens group, a zoom lens group, and a beam splitting device.
  • the light splitting device may be a beam splitting prism, a beam splitting grating, a binary optical element, or the like. After the light beam is emitted from the laser light source, it is split into three beams through the optical path 122. The three beams are respectively incident on the growth chamber 101 through the two mirrors 123 and 123, and are formed on the surface of the substrate material 200. Interfere with the image.
  • a reflection high energy electron diffraction (RHEED) device is also provided outside the growth chamber 101, and the reflection high energy electron diffraction (RHEED) device is provided.
  • An electron beam emitting gun 112 and a diffraction display window 113 are included.
  • the diffraction display window 113 is disposed on the cavity wall of the growth chamber 101.
  • the diffraction display window 113 displays an electron beam diffraction image, and when the surface of the epitaxial layer is uneven, the diffraction image exhibits a corresponding change.
  • FIG. 4 shows an apparatus for fabricating a quantum dot material according to a second embodiment of the present invention.
  • the light incident window 211 on the wall of the growth chamber 201 is also increased to four, and each is equally spaced around the cavity wall of the growth chamber 201, so that four bundles are used. After passing through the four windows 211, the light rays are gathered together at intervals of 90 degrees to form a four-beam interference image. Others that are identical to the first embodiment are not described in expansion.
  • FIG. 5 is a flow chart of the method for fabricating the quantum dot material of the present invention. As shown, the method of making includes the steps of:
  • S12 Heating the bottom of the village, maintaining the bottom of the village at the first temperature, and starting to deposit an epitaxial layer on the surface of the village by epitaxial method.
  • the epitaxial layer has a different lattice constant than the substrate material, and at the first temperature, the critical thickness of the atomic aggregation effect generated by the epitaxial layer to release the lattice stress is the first thickness.
  • the epitaxial method is molecular beam epitaxy or metal-organic chemical vapor deposition (MOCVD).
  • the interference image is a periodic lattice in which the temperature of the epitaxial layer rises to a second temperature at the interference enhancement region of the periodic lattice, i.e., at the bright spot.
  • the critical thickness of the atomic aggregation effect of the epitaxial layer to release the lattice stress is a third thickness, and the third thickness is smaller than the thickness of the epitaxial layer at this time, that is, the second thickness.
  • the epitaxial layer continues to be deposited.
  • the thickness of the epitaxial layer may exceed the first thickness due to increasing, the atomic aggregation generated in the previous step has provided the "window" required to release the lattice stress on the surface of the entire epitaxial layer, and thus These places called “seeds” continue to grow as the thickness of the epitaxial layer grows, and eventually form quantum dots on the surface of the epitaxial layer.
  • the laser light source used in the present invention is preferably a laser light source in the form of a short pulse. Because the distance between the bright spot and the bright spot is usually very close, the distance between the bright spot and the bright spot is only a width of 100 nanometers. Therefore, if the heating time is long, it is easy to conduct heat due to heat conduction, so that the temperature of all surrounding areas also rises. A temperature field with a significant temperature difference. Under the action of the short pulse laser source, since the time of one pulse is very short, it is much smaller than the time required for thermal diffusion, so the correspondence between the temperature distribution of the surface of the epitaxial layer and the interference image can be ensured.
  • the present invention provides a method and apparatus for fabricating a quantum dot material, which adds an optical device capable of generating an interference image to an existing epitaxial device, so that the substrate is epitaxially extended at the same time.
  • An interference image is applied to the layer.
  • a regularly distributed temperature field is formed on the epitaxial layer, so that the epitaxial layer begins to form an atomic aggregation phenomenon at a higher temperature point, and no atomic aggregation occurs in a relatively low temperature region.
  • the position of the quantum dot can be artificially controlled, and a long-range ordered quantum dot fabrication method can be realized, and the growth of the quantum dot and the smooth surface SK growth mode can be realized.
  • the mechanism is the same, so that defect-free growth can be achieved.

Abstract

一种量子点材料制作装置和制作方法。该制作装置（10）通过在现有外延装置（110）中添加了可以产生干涉图像的光学装置（120），使得衬底（200）在进行外延的同时，在外延层上施加了一个干涉图像。通过该干涉图像，在外延层上形成一个规则分布的温度场，使得外延层在温度较高的点位上开始形成原子聚集现象，而在温度相对较低的区域则没有原子聚集。由此，根据外延表面温度的分布情况，能够人为控制量子点产生的位置而不引入缺陷，实现一种无缺陷的长程有序的量子点制作。

Description

一种量子点材料的制作装置及制作方法
本申请要求于 2011 年 08 月 05 日提交中国专利局、 申请号为 201110224270.7、发明名称为"一种量子点材料的制作装置及制作方法"的中 国专利申请的优先权， 其全部内容通过引用结合在本申请中。
技术领域
本发明涉及低维半导体材料的制造技术领域， 尤其涉及一种量子点半 导体材料的制作装置和制作方法。
背景技术
半导体量子点低维纳米结构材料由于其独特的电子结构和态密度， 呈 现出优异的光电特性， 在未来纳米电子学， 光电子学， 生命科学和量子计 算等领域有着极其广泛的应用前景。 理论分析表明， 量子点激光器在很多 方面要比量子阱激光器具有更优越的性能。 如更高增益、 更低阈值电流、 更高量子效率及热稳定性更好等。 此外利用量子点电子的 "遂穿" 效应， 可以精确控制进入或离开量子点电子数目至单电子精度， 从而可制作单电 子晶体管。 量子点还有望应用于固态量子计算、 垂直入射光探测器等。
s-κ模式自组织生长是目前国内外科学家研究最多的， 且具有重要应 用价值的量子点材料制备方法。 其主要原理如下： 不同于村底晶格常数的 半导体材料在分子束外延 (Molecular Beam Epitaxy； MBE)等外延生长过程 中， 生长方向的晶格常数不同于村底平面， 这样就会产生晶格应力。 应力 积聚到一定的程度就会通过表面原子迁移和聚集， 或者产生失配位错， 来 释放这些应力。 前者聚集成堆的原子团在生长过程中将长大并被掩埋在随 后生长的外延材料中， 形成量子点。 由于应力释放需要而形成的初始原子 团， 就是量子点生长的"种子"， 随后的量子点就是这些"种子"长大形成的。 而这些"种子"的形成是热力学统计涨落的结果， 其形成位置、 速度和大小 完全是随机的。 这就是所谓量子点的 S-K动态随机生长机制。 如图 1A所示。目前应用于器件的量子点都是如图 1A的 S-K模式外延 生长模式生长的"无序"自组织生长（动力学随机生长） 的量子点。 优点是 无缺陷， 可以用于实际器件的制备， 并且被证明性能明显优于同类器件的 其它材料。 然而， 许多关键参数， 诸如： 量子点的尺寸和空间分布是随机 的和不可控的， 可重复生产性差， 难以实现产业化。 如此生长的量子点无 法用来制备量子信息器件， 即使从规模器件工艺制备的大量器件中有幸发 现少量能工作的器件， 其各个器件的性能也会有^艮大的差别。 这种"无序" 量子点由于增益谱太宽， 也很难制备比较大功率的激光器。 图 1B中"短程 有序"的量子点是通过在原位向村底喷射刻蚀气体，在村底表面刻蚀出一些 微孔， 然后再在这些微孔的位置生长出量子点双胞胎， 与"无序"自组织的 量子点相比， 有一定的有序性， 然而在刻蚀气体刻蚀出的微孔里会有很多 刻蚀缺陷，这些缺陷会在生长量子点的过程中被保留甚至放大。图 1C中"长 程有序 "的量子点是通过事先将村底用常规纳米制造技术，刻蚀出纳米图样 模板， 然后再在这个模板上外延生长量子点。 常规纳米结构化引入的缺陷 无论从大小还是规模都比刻蚀气体刻蚀出微孔而引发的缺陷要大。"短程有 序"和"长程有序"的量子点里的缺陷都使其制备的器件无法工作。
因此， 如何制备大面积长程有序分布的无缺陷或低缺陷密度的量子点 成为了目前半导体低维纳米结构材料的前沿和热点研究领域。
发明内容
有鉴于此， 本发明了提出一种制作量子点材料的装置和方法， 可以在 进行外延的过程中， 即时的控制量子点的生长位置， 不仅可以制作出长程 有序的量子点材料， 而且因为无需对村底进行任何刻蚀处理， 因此不会引 起因刻蚀而带来的缺陷问题。
根据本发明的目的提出的一种量子点制作装置， 包括外延装置以及用 于产生干涉图像的光学装置， 所述外延装置包括生长室， 所述生长室为真 空腔室， 用于放置一村底材料， 该生长室腔壁上设有可供光线射入的多个 窗口， 所述光学装置包括激光光源和调制光路， 光束从激光光源射出后， 经所述调制光路分成多束光， 该多束光分别通过所述多个窗口后射入生长 室中， 并在所述村底材料表面形成干涉图像。
可选的， 所述多个窗口为三个， 各自等间距的分布在所述生长室的腔 壁四周。
可选的， 所述光束从激光光源射出后， 经调制光路分成三束光， 该三 束光分别通过上述三个窗口后射入生长室中， 并在村底材料表面形成三光 束干涉图像。
可选的， 所述多个窗口为四个， 各自等间距的分布在所述生长室的腔 壁四周。
可选的， 所述光束从激光光源射出后， 经调制光路分成四束光， 该四 束光分别通过上述四个窗口后射入生长室中， 并在村底材料表面形成四光 束干涉图像。
可选的， 所述激光光源为脉沖激光光源。
根据本发明的目的同时提出的一种量子点材料的制作方法， 采用上述 的量子点材料制作装置进行制作， 包括步骤：
1 )将一村底材料装载到生长室中， 对生长室进行抽真空；
2)对村底加热， 使村底维持在第一温度下， 并开始用外延方法在所述 村底表面沉积一外延层；
3)控制沉积速率，使沉积在村底材料表面的外延层厚度达到第二厚度， 所述第二厚度小于第一温度下的临界厚度；
4)打开激光光源， 在外延层表面形成一干涉图像， 所述干涉图像使得 外延层的部分区域温度升高至第二温度， 该第二温度下的临界厚度小于第 二厚度；
5) ^掉干涉图像后， 继续沉积外延层， 最终在外延层表面形成量子点。 可选的，所述干涉图像为周期性点阵，在该周期性点阵的干涉加强区， 外延层的温度升高至第二温度。
通过在现有的外延装置中添加了可以产生干涉图像的光学装置， 使得 村底在进行外延的同时，在外延层上施加一个干涉图像。通过该干涉图像， 在外延层上形成一个规则分布的温度场， 使得外延层在温度较高的点位上 开始形成原子聚集现象， 而在温度相对较低的区域则没有原子聚集。 如此 一来， 根据外延测表面温度的分布情况， 就能人为的控制量子点产生的位 置， 实现一种长程有序的量子点制作方法。
附图说明 为了更清楚地说明本发明实施例或现有技术中的技术方案， 下面将对 实施例或现有技术描述中所需要使用的附图作筒单地介绍， 显而易见地， 下面描述中的附图仅仅是本发明的一些实施例， 对于本领域普通技术人员 来讲， 在不付出创造性劳动的前提下， 还可以根据这些附图获得其他的附 图。
图 1 A- 1 C分别为现有的量子点材料上的量子点分布图；
图 2是利用三光束干涉产生的干涉图像的温度分布图；
图 3是本发明的第一实施方式的制作量子点材料的装置；
图 4是本发明的第二实施方式的制作量子点材料的装置；
图 5是本发明量子点材料制作方法流程图。
具体实施方式
下面将结合本发明实施例中的附图， 对本发明实施例中的技术方案进 行清楚、 完整地描述， 显然， 所描述的实施例仅仅是本发明一部分实施例， 而不是全部的实施例。 基于本发明中的实施例， 本领域普通技术人员在没 有做出创造性劳动前提下所获得的所有其他实施例， 都属于本发明保护的 范围。
正如背景技术部分所述， 多数量子点器件都要求量子点材料本身是无 缺陷 （或低缺陷密度） 、 尺寸和空间分布有序、 均匀。 而现有的制作量子 点的外延方法中， 采用 S-K模式自组织生长方式形成的量子点， 由于其生 长过程呈现随机性， 因此以这种方式取得的量子点的分布是无序的。 而通 过在村底材料表面制作规则图形后生长的量子点， 虽然具有一定范围内的 长程有序，但是在制备过程中，容易导致基体损伤并产生大量的晶体缺陷， 大大影响了量子点的光电特性。
有鉴于此， 本发明提出了一种量子点材料的制作方法。 该制作方法利 用在外延生长膜层的同时， 在膜层表面施加一个规则分布的温度场， 使得 膜层表面温度较高的点位比在其它温度较低的区域更快的产生原子聚集的 效应， 量子点的 "种子" 在温度场的引导下， 形成规则的分布， 从而制作 出长程有序的量子点材料。
为了便于理解，下面先对本发明的技术方案所依据的原理做筒单介绍。 在量子点的形成过程中， 外延生长经历了两个阶段： "种子" 形成前 村底平面上原子层逐层生长的二维（2D )模式， "种子" 形成时和随后的 量子点生长的三维（3D )模式（因为量子点突出于生长平面） 。 从 2D 到 3D的生长的临界点时的原子层厚度叫临界厚度。
已有大量试验表明， 温度是影响量子点分子束外延（MBE )生长过程 中临界厚度的一个关键因素， 以在 GaAs村底外延生长 InAs层为例，低温 (低于 430°C )时的临界厚度是高温（高于 460 °C )时临界厚度的 2.5倍以 上。 也就是说， 在不同温度下， 产生原子聚集效应所需要的膜层厚度是不 一样的。 往往在低温环境下所需要的临界厚度要比高温环境下的大， 且这 里的低温和高温只是一个相对的概念， 两者之间从几十度到几百度都是有 可能的。
根据上述原理， 如果能在村底上生长外延层的同时， 在外延层表面形 成温度不一的规则分布， 使部分区域的温度达到形成第一临界厚度需要的 相对较高温度， 而其它部分区域的温度只达到形成第二临界厚度需要的相 对较低温度。 那么可以预见， 当外延层的厚度达到第一临界厚度且小于第 二临界厚度时， 则在相对较高温度的区域便已开始有原子集聚， 而在相对 较低温度的其它区域还不足以使原子开始集聚。 如此一来， 通过温度的变 化便能人为的引导量子点的产生区域， 使量子点产生具有规则的长程有序 分布。
因此， 本发明的关键在于如何在外延层上提供规则分布的温度场。 直写激光干涉光刻 ( direct writing laser interference lithography： DW-LIL )技术是无掩模、 可直接刻写、 高效率（立等可取）、 图案（电脑） 程控变换、 无沾污、 无接触、 大面积、 低成本和环境要求低的创新技术。 激光干涉光刻的基本原理是利用两束或两束以上的相干激光叠加照射在样 品表面， 产生干涉图样。 叠加区域的电场为各相干光束电场的矢量和， 不 同的电场分布对应着不同的干涉图样。 由双光束干涉引起的干涉图像为明 暗相间的条文状图像， 而由三光束干涉或四光束干涉引起的干涉图像则为 六方体或四方体形状的周期性点阵。
通常情况下， 直写激光干涉光刻是利用干涉图像的光学性质， 使光敏 材料在干涉加强区即出现明亮条文或明亮斑点的地方发生变异， 从而在材 料表面形成刻蚀图样。 有一些特殊的应用中， 也可以直接利用激光光束的 高热量对材料表面进行破坏性打孔从而形成表面图形的。 在这种情况下， 干涉图像的温度分布就显得极为重要。 请参见图 2, 图 2是利用四光束干 涉产生的干涉图像的温度分布图。 如图所示， 温度最高的区域与温度最低 的区域之间温度差超过 1000°C以上。这说明，通过调节光源激光器的功率， 可以实现温差从 0 到 1000°C以上的周期性温度调制场。因此利用激光的多 光束干涉图像， 可以实现一个规则的、 温度变化范围极广的温度场， 从而 解决本发明的温度控制。
下面将结合附图对本发明的实施方式做具体的说明。
请参见图 3 , 图 3是本发明的第一实施方式的制作量子点材料的装置。 如图所示， 本发明的量子点制作装置 10, 包括外延装置 110以及用于产生 干涉图像的光学装置 120。 外延装置 110包括生长室 101 , 所述生长室 101 为真空腔室， 村底材料 200放置在该在生长室 101中。 该生长室 101腔壁 上设有多个可供光线射入的窗口 111 , 由于在本实施方式中， 采用的是三 光束干涉，因此此处的窗口 111为 3个，且各自等间距的分布在生长室 101 的腔壁四周， 使得 3束光线分别经过该三个窗口 111后， 以两两间隔 120 度汇聚在一起形成三光束干涉图像。
光学装置 120包括激光光源 121和光路 122。 在光路 122中设有各种 调节和调制光路用的光学元器件， 比如准直透镜组、 缩放透镜组以及分光 器件。 其中分光器件可以是分光棱镜、 分光光栅、 二元光学元件等。 光束 从激光光源射出后， 经光路 122分成三束光， 该三束光分别经由两个反射 镜 123、 123，后， 从窗口 111中射入生长室 101 , 并在村底材料表面 200上 形成干涉图像。
进一步的， 在进行分子束外延生长过程中， 往往需要对原子的生长过 程进行监控， 因此在生长室 101的外部还设有反射高能电子衍射 (RHEED) 装置， 该反射高能电子衍射 (RHEED)装置包括电子束发射枪 112以及衍射 显示窗口 113。 其中， 衍射显示窗口 113设置在生长室 101的腔壁上， 该 衍射显示窗口 113显示电子束衍射图像， 当外延层表面出现不平整时， 衍 射图像就呈现出相应的变化。
请参见图 4, 图 4是本发明的第二实施方式的制作量子点材料的装置。 在该实施方式中， 由于采用四光束干涉， 因此其生长室 201腔壁上的光线 射入窗口 211也增加至 4个， 且各自等间距的分布在生长室 201的腔壁四 周，使得 4束光线分别经过该四个窗口 211后， 以两两间隔 90度汇聚在一 起形成四光束干涉图像。 其他与第一实施方式相同之处不在做展开描述。
请参见图 5, 图 5是本发明量子点材料制作方法流程图。 如图所示， 该制作方法包括步骤：
S11 : 首先将一村底材料装载到生长室中， 对生长室进行抽真空。
S12: 对村底加热， 使村底维持在第一温度下， 并开始利用外延方法在 村底表面沉积一外延层。其中所述外延层具有与村底材料不同的晶格常数， 在所述第一温度下， 该外延层为释放晶格应力而产生的原子聚集效应的临 界厚度为第一厚度。 所述外延方法为分子束外延或者金属有机化合物化学气相淀积 (Metal- organic Chemical Vapor Deposition, MOCVD)„
S13:控制沉积速率，使沉积在村底材料表面的外延层厚度达到第二厚 度， 所述第二厚度小于第一厚度。 此时， 外延层尚未开始产生原子聚集。
S14: 打开激光光源， 在外延层表面形成一干涉图像。 所述干涉图像为 周期性点阵， 在该周期性点阵的干涉加强区， 即光亮点处， 外延层的温度 升高至第二温度。 在该第二温度下， 外延层为释放晶格应力而产生的原子 聚集效应的临界厚度为第三厚度， 所述第三厚度小于此时的外延层厚度， 即第二厚度。
此时， 在光亮点处的外延层表面， 因厚度已经达到需要释放晶格应力 的临界厚度， 因此在这些区域瞬间出现原子的聚集现象， 表现为由原先平 整的单分子层表面出现一个个原子团， 这些原子团即为以后生长量子点所 需的 "种子" 。 此时若观察电子衍射屏， 会看到电子衍射图像会出现明显 的变动， 这是因为原先平整的外延层表面出现了一个个凸点， 电子束打到 这些凸点上时， 就会出现比较明显的衍射现象。
S15: ^掉干涉图像后， 继续沉积外延层。 此时， 尽管外延层的厚度会 因不断增加而超过第一厚度， 但是， 由上一步骤中产生的原子聚集处已经 提供了整个外延层表面释放晶格应力所需的 "窗口"， 因此在这些称为 "种 子" 的地方会随着外延层厚度的增长也不断生长， 并最终在外延层表面形 成量子点。
值得一提的是， 在本发明中使用的激光光源， 最好是短脉沖形式的激 光光源。 因为形成的干涉图像中， 亮点与亮点之间的距离通常非常近， 仅 有百纳米级的宽度， 因此如果加热时间长， 很容易因热传导， 使得周围所 有区域的温度也上升， 这样就无法实现具有明显温度差的温度场。 而在短 脉沖激光光源的作用下， 由于一个脉沖的时间非常短， 远远小于热扩散所 需的时间， 因此可以保证外延层表面的温度分布与干涉图像之间的对应关 系。 综上所述， 本发明提供一种制作量子点材料的制作方法和装置， 该装 置在现有的外延装置中添加了可以产生干涉图像的光学装置， 使得村底在 进行外延的同时， 在外延层上施加一个干涉图像。 通过该干涉图像， 在外 延层上形成一个规则分布的温度场， 使得外延层在温度较高的点位上开始 形成原子聚集现象， 而在温度相对较低的区域则没有原子聚集。如此一来， 根据外延层表面温度的分布情况， 就能人为的控制量子点产生的位置， 实 现一种长程有序的量子点制作方法， 该方法生长的量子点与光滑表面 S-K 生长模式的生长机理是一样的， 因而可以实现无缺陷生长。
对所公开的实施例的上述说明，使本领域专业技术人员能够实现或使 用本发明。 对这些实施例的多种修改对本领域的专业技术人员来说将是显 而易见的， 本文中所定义的一般原理可以在不脱离本发明的精神或范围的 情况下， 在其它实施例中实现。 因此， 本发明将不会被限制于本文所示的 实施例，而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。

Claims

1、 一种量子点材料制作装置， 其特征在于： 包括外延装置以及用于产 生干涉图像的光学装置， 所述外延装置包括生长室， 所述生长室为真空腔 室，用于放置一村底材料，该生长室腔壁上设有可供光线射入的多个窗口， 所述光学装置包括激光光源和调制光路， 光束从激光光源射出后， 经所述 调制光路分成多束光， 该多束光分别通过所述多个窗口后射入生长室中， 权
并在所述村底材料表面形成干涉图像。
2、 如权利要求 1所述的量子点利 _材料制作装置， 其特征在于： 所述多个
1
窗口为三个， 各自等间距的分布在所述 o要生长室的腔壁四周。
3、 如权利要求 2所述的量子点材料制作装置， 其特征在于： 所述光束 求
从激光光源射出后， 经调制光路分成三束光， 该三束光分别通过上述三个 窗口后射入生长室中， 并在村底材料表面形成三光束干涉图像。
4、 如权利要求 1所述的量子点材料制作装置， 其特征在于： 所述多个 窗口为四个， 各自等间距的分布在所述生长室的腔壁四周。
5、 如权利要求 4所述的量子点材料制作装置， 其特征在于： 所述光束 从激光光源射出后， 经调制光路分成四束光， 该四束光分别通过上述四个 窗口后射入生长室中， 并在村底材料表面形成四光束干涉图像。
6、 如权利要求 1所述的量子点材料制作装置， 其特征在于： 所述激光 光源为脉沖激光光源。
7、一种量子点材料的制作方法，采用如权利要求 1至 6中任意一项所 述的量子点材料制作装置进行制作， 其特征在于， 包括步骤：
1 )将一村底材料装载到生长室中， 对生长室进行抽真空；
2)对村底加热， 使村底维持在第一温度下， 并开始用外延方法在所述 村底表面沉积一外延层；
3)控制沉积速率，使沉积在村底材料表面的外延层厚度达到第二厚度， 所述第二厚度小于第一温度下的临界厚度； 4)打开激光光源， 在外延层表面形成一干涉图像， 所述干涉图像使得 外延层的部分区域温度升高至第二温度， 该第二温度下的临界厚度小于第 二厚度；
5) ·^掉干涉图像后， 继续沉积外延层， 最终在外延层表面形成量子点。
8、 如权利要求 7所述的量子点材料的制作方法， 其特征在于： 所述干 涉图像为周期性点阵， 在该周期性点阵的干涉加强区， 外延层的温度升高 至第二温度。
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