WO2024011842A1 - 一种可控温度梯度的晶体生长装置及方法 - Google Patents

一种可控温度梯度的晶体生长装置及方法 Download PDF

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WO2024011842A1
WO2024011842A1 PCT/CN2022/138862 CN2022138862W WO2024011842A1 WO 2024011842 A1 WO2024011842 A1 WO 2024011842A1 CN 2022138862 W CN2022138862 W CN 2022138862W WO 2024011842 A1 WO2024011842 A1 WO 2024011842A1
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temperature gradient
crucible
heater
crystal
crystal growth
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PCT/CN2022/138862
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English (en)
French (fr)
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党冀萍
孙聂枫
史艳磊
徐成彦
秦敬凯
王书杰
刘峥
付莉杰
邵会民
刘惠生
王阳
李晓岚
马春雷
王维
康永
李亚旗
赵红飞
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中国电子科技集团公司第十三研究所
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Publication of WO2024011842A1 publication Critical patent/WO2024011842A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
    • C30B11/007—Mechanisms for moving either the charge or the heater
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
    • C30B11/003—Heating or cooling of the melt or the crystallised material
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
    • C30B11/006—Controlling or regulating

Definitions

  • the present invention relates to the field of semiconductor, optical crystal and metal crystal preparation, and in particular to devices and methods for preparing crystals with high yield, low cost and low stress using vertical Bridgman method and vertical gradient solidification method.
  • the main growth methods used for the preparation of semiconductor and optical crystals are: Czochralski method, vertical gradient solidification (VGF), vertical Bridgman method (VB), etc.
  • the Czochralski method is a more traditional single crystal preparation method, which is characterized by high growth temperature gradient and high yield of single crystals.
  • the crystals prepared by this method have high stress, high density of defects such as dislocations, and the crystals are easily broken.
  • the vertical gradient solidification method and the vertical Bridgman method growth method are characterized by low growth temperature gradient and small temperature gradient of the prepared crystals.
  • the temperature gradient during growth is too low, it is easy to cause instability of the growth interface and the growth of crystal defects such as twins and polycrystals, resulting in a reduction in crystal yield.
  • crystals prepared by these two growth methods remains high, especially for crystals such as indium phosphide, gallium phosphide, zinc germanium phosphide, and indium antimonide that are prone to defects such as twins and polycrystals or are easily broken.
  • the temperature gradient during the growth process has the greatest impact on the quality of the crystal.
  • the temperature gradient in the crystallized crystal determines the crystal stress and dislocation density.
  • the greater the temperature gradient in the crystal the greater the crystal stress and the higher the dislocation density; the temperature gradient in the melt determines whether the crystal growth interface is lost.
  • Stable especially for long-size compound materials and elemental materials containing dopants, the influence is great.
  • the temperature gradient in the melt is small, and it is easy to cause supercooling of the components due to the deviation of the components at the front edge of the solid-liquid interface, resulting in interface failure. stability and the occurrence of twins and polycrystals.
  • the traditional way to control the temperature gradient is to set up segmented heaters outside the crucible, and each segment can independently control the heating temperature.
  • the fluidity of the melt is very good under high temperature conditions, which results in very good uniformity.
  • the temperature uniformity caused by thermal convection is easy to maintain.
  • the eddy currents may rotate or circulate in a large direction, making it difficult to establish a temperature gradient.
  • the purpose of the invention is to solve the problem of low yield in vertical gradient solidification (VGF) and vertical Bridgman (VB) crystal growth.
  • a crystal growth device with a controllable temperature gradient including a crucible, a crucible holder, a crucible rod, a heater I, a heater II, a heater III around the crucible and supporting thermocouples.
  • a seed crystal tank is set at the bottom of the crucible. The key is that, The growth device also includes a melt temperature gradient control mechanism and a crystal temperature gradient control mechanism.
  • the melt temperature gradient control mechanism is arranged inside the crucible and includes a lifting rod. , Connect the lifting rod.
  • the heating plate has built-in heating wire and thermocouple IV.
  • the crystal temperature gradient control mechanism includes a constant temperature chiller and a cold water circulation pipeline connected to the constant temperature chiller.
  • the cold water circulation pipeline is close to the bottom of the seed crystal tank.
  • the heating plate has a concave arc surface.
  • the cold water circulation pipeline includes an outlet pipe and a return pipe connected to the constant temperature chiller.
  • the crucible rod is a hollow tube.
  • the outlet pipe enters the crucible rod and extends to the top of the crucible rod.
  • the return pipe is connected to Crucible rod and thermostatic chiller.
  • the present invention also proposes a crystal growth method with a controllable temperature gradient.
  • the growth method includes the following steps:
  • Step 1 Use deionized water to clean the material to ensure that there is no contamination on the surface of the material;
  • Step 2 Place the seed crystal into the seed crystal tank at the bottom of the crucible;
  • Step 3 Lower the melt temperature gradient control mechanism to the bottom of the crucible;
  • Step 4 Load the materials into the crucible
  • Step 5 Turn on the constant temperature chiller and set the chiller flow rate to 10L/min;
  • Step 6 Turn on heater I, heater II, and heater III, and set the temperatures to 30°C, 20°C, and 10°C higher than the melting point of the material respectively;
  • Step 7 Turn on the heating wire so that the thermocouple IV reaches 3-15°C above the melting point of the material
  • Step 8 Keep the temperature constant for 30-60 minutes to ensure that all the materials in the crucible are melted
  • Step 9 Reduce the power of heater I, heater II, and heater III, and set the temperatures to 20°C, 10°C, and 5°C higher than the melting point of the material respectively;
  • Step 10 Gradually increase the water supply flow of the constant temperature chiller until it increases to 30L/min, and the water flow rate increases at 0.1L/min;
  • Step 11 Raise the melt temperature gradient control mechanism with a pulling speed of 2-5mm/h; set the cooling rate of heater I, heater II and heater III to 1-3°C/h;
  • Step 12 The melt temperature gradient control mechanism leaves the melt and the crystal growth ends
  • Step 13 Heater I, Heater II, and Heater III are cooled down at a cooling rate of 100°C/h to complete the cooling of the crystal.
  • step 11 the distance between the heating plate and the solid-liquid interface is maintained at 5-15 mm.
  • a melt temperature gradient control mechanism and a crystal temperature gradient control mechanism are added to the device, and the purpose of the invention is achieved through precise control.
  • the present invention sets a movable heating device in the melt, improves the temperature gradient in the melt by accurately controlling the position and temperature of the heating device, stabilizes the crystal growth interface, and reduces the probability of twins and polycrystals. ; Cooling water with precise flow and basically constant temperature is introduced into the crucible rod, and the temperature gradient at the seed crystal can be controlled by adjusting the water flow. The growth of crystals with high quality and high yield is achieved through precise control of the temperature gradient in the melt and at the seed crystal.
  • Figure 1 is a diagram of the device composition after loading is completed.
  • Figure 2 is a diagram of the device state after the material is completely melted.
  • Figure 3 is a device status diagram during the crystal growth process.
  • Figure 4 is a schematic diagram of the melt temperature gradient control mechanism.
  • Figure 5 is a comparison of the temperature gradient curves of the front edge of the solid-liquid interface when synthesizing indium phosphide according to the present invention and the traditional method.
  • thermocouple I 1 is thermocouple I
  • 2 is thermocouple II
  • 3 is thermocouple III
  • 4 is heater I
  • 5 is heater II
  • 6 is heater III
  • 7 is crucible
  • 8 is seed tank
  • 9 is Materials
  • 10 is seed crystal
  • 11 is return pipe
  • 12 is crucible rod
  • 13 is cooling water
  • 14 is outlet pipe
  • 15 is thermocouple IV
  • 16 is lift rod
  • 17 is heating wire
  • 18 constant temperature chiller
  • 19 19 is the growing crystal
  • 20 is the crucible holder.
  • a crystal growth device with a controllable temperature gradient see Figure 1, including a crucible 7, a crucible holder 20, a crucible rod 12, a heater I4, a heater II5, a heater III6 on the periphery of the crucible and a matching thermocouple I1 and a thermocouple II2, thermocouple III3; a seed crystal tank 8 is provided at the bottom of the crucible 7.
  • the heater and thermocouple are a coupled control pair, and the power of the corresponding heater is adjusted by testing the temperature of the thermocouple.
  • Crucible 7 is made of quartz, boron nitride and other materials, and is used to place seed crystals, crystals, melts and covering agents.
  • the crucible holder is made of alumina thermal insulation cotton, carbon felt and other materials to insulate the bottom of the crucible and the seed crystal.
  • the growth device also includes a melt temperature gradient control mechanism and a crystal temperature gradient control mechanism.
  • the melt temperature gradient control mechanism is set inside the crucible 7 and includes a lifting rod 16 and a heating plate connected to the lifting rod 16. It is made of quartz or boron nitride material; the heating plate has a built-in heating wire 17 and a thermocouple IV 15, as shown in Figure 4.
  • the heating plate is circular when viewed from below, as shown in Figure 4, with a diameter close to the inner diameter of the crucible 7; the heating plate has a concave arc surface, and its shape is similar to the expected shape of the crystal solid-liquid interface.
  • the heating wire 17 and the thermocouple IV 15 are a coupled control pair, and the power of the corresponding heating wire is adjusted through the thermocouple test temperature, so that the thermocouple reaches the preset temperature.
  • the lifting rod 16 is connected to a driving device (not shown in the figure), so that the heating plate can move up and down at a speed of 1-50mm/h, and the speed is adjustable.
  • the crystal temperature gradient control mechanism includes a constant temperature chiller 18 and a cold water circulation pipeline connected to the constant temperature chiller 18.
  • the cold water circulation pipeline is close to the bottom of the seed crystal tank 8, with a distance of 3-10 mm.
  • the constant temperature chiller 18 provides cold water at 14-17°C, with a water temperature control accuracy of ⁇ 0.5°C, a maximum water flow of 100L/min, the flow rate is adjustable from 10-100L/min, and a flow control accuracy of ⁇ 0.1L/min.
  • the cold water circulation pipeline includes an outlet pipe 14 and a return pipe 11 connected to the constant temperature chiller 18.
  • the crucible rod 12 is a hollow tube as a part of the cold water circulation pipeline.
  • the outlet pipe 14 enters the crucible rod 12 and extends to the crucible rod 12.
  • the return pipe 11 communicates with the crucible rod 12 and the constant temperature chiller 18 .
  • the cooling water 13 is pumped out from the constant temperature chiller 18, enters the inside of the crucible rod 12 through the outlet pipe 14, reaches the top of the crucible rod 12, and then flows into the constant temperature chiller through the return pipe 11 from the middle position between the crucible rod 12 and the outlet pipe 14. Chiller18.
  • the outlet pipe 14 and the return pipe 11 are made of stainless steel and covered with thermal insulation materials.
  • the inner diameter of the pipe is 10-20mm.
  • the distance between the top of the hollow part of the crucible rod 12 and the seed crystal groove 8 is 3-10 mm.
  • the present invention also proposes a crystal growth method with a controllable temperature gradient.
  • the growth method includes the following steps:
  • Step 1 Use deionized water to clean the material 9 to ensure that the surface of the material 9 is free of contamination.
  • the material 9 here is a semiconductor compound, such as indium phosphide, gallium phosphide, zinc germanium phosphide, indium antimonide, etc.
  • Step 2 Place the seed crystal 10 into the seed crystal tank 8 at the bottom of the crucible.
  • Step 3 Drive the lifting rod 16 through the driving device to lower the melt temperature gradient control mechanism to the bottom of the crucible 7 .
  • Step 4 Load material 9 into crucible 7.
  • Step 5 Turn on the constant temperature chiller 18, and set the flow rate of the chiller to 10L/min.
  • Step 6 Turn on heater I4, heater II5, and heater III6, and set the temperatures to be 30°C, 20°C, and 10°C higher than the melting point of material 9 respectively.
  • Step 7 Turn on the heating wire 17 so that the thermocouple IV 15 reaches 3-15°C above the melting point of the material 9.
  • Step 8 Wait until the temperatures displayed by thermocouple I1, thermocouple II2, and thermocouple III3 reach the set temperature respectively. Keep the temperature constant for 30-60 minutes to ensure that all material 9 in crucible 7 is melted.
  • Step 9 Reduce the power of heater I4, heater II5, and heater III6, and set the temperatures to 20°C, 10°C, and 5°C respectively higher than the melting point of material 9. At this time, the melt can still be ensured to remain in a molten state.
  • Step 10 Gradually increase the water supply flow of the constant temperature chiller until it increases to 30L/min.
  • the water flow rate increases at 0.1L/min to meet the latent heat release requirements of crystallization.
  • the melt 9 close to the seed crystal 10 begins to adhere to the seed crystal 10 and solidify according to the seed crystal lattice arrangement.
  • Step 11 Raise the melt temperature gradient control mechanism, and the pulling speed is 2-5mm/h. Set the cooling rate of heater I4, heater II5, and heater III6 to 1-3°C/h, so that the melt gradually solidifies.
  • the pulling speed determines the growth rate of the crystal 19 to a certain extent, and can increase the temperature gradient in the melt at the solid-liquid interface front, ensuring that the melt thickness at the interface front is at a lower value (generally requires a temperature gradient control mechanism and a solid-liquid interface The distance is 5-15mm) to ensure the stability of crystal growth.
  • the temperature gradient in the melt can be easily controlled and data obtained.
  • Temperature gradient (control unit thermocouple temperature - material melting point)/the distance between the solid-liquid interface and the temperature gradient control unit. In the traditional method of controlling the temperature gradient, the heater is outside the crucible, and it is difficult to control the temperature gradient of the melt and obtain actual gradient data.
  • the solid-liquid interface refers to the contact surface between the upper surface of the crystal 19 (solid) and the melt, and is the interface for crystal growth.
  • the temperature control unit is close to the growth interface and has a very strong ability to control the solid-liquid interface. Therefore, the temperature Gradient is easier to maintain and control than existing techniques. Moreover, as the solid-liquid interface advances toward the melt, the distance between the solid-liquid interface and the temperature control unit can be kept unchanged, thereby ensuring a stable temperature gradient control effect during the entire crystal growth period. At the same time, during the crystal growth process, the heater outside the crucible and the heating plate rise and cool down simultaneously (1-3°C/h), which also ensures the control of the temperature gradient.
  • the temperature of the solid-liquid interface (the position where the abscissa is 0) is the melting point of indium phosphide (1062°C).
  • the heating plate and the solid A basically linear temperature gradient is established between the liquid interface (in this example, the heating plate is 9 mm away from the solid-liquid interface, and the temperature is set to 11°C).
  • the curve using the traditional method is an ideal situation: the external heater is at the solid-liquid interface.
  • Step 12 The melt temperature gradient control mechanism leaves the melt, the melt is completely solidified, and the crystal growth ends.
  • Step 13 Heater I4, heater II5, and heater III6 are cooled down at a cooling rate of 100°C/h to complete the crystal cooling.
  • a covering agent that has a density lower than the material and does not stain the material can be installed.
  • Boron oxide is generally used (not shown in the figure).

Abstract

一种可控温度梯度的晶体生长装置及方法，涉及半导体、光学晶体及金属晶体制备领域，晶体生长装置包括坩埚及配套组件、熔体温度梯度控制机构、晶体温度梯度控制机构；熔体温度梯度控制机构设置在坩埚内部，包括升降杆、加热板；晶体温度梯度控制机构包括恒温冷水机、冷水循环管路。生长方法包括在晶体生长期间，逐渐增加恒温冷水机供水流量，直至增加至30L/min；上升熔体温度梯度控制机构，提拉速度为2‑5mm/h。在熔体中设置可移动的加热装置，通过精准控制加热装置的位置和温度来改善熔体中的温度梯度；在坩埚杆内部通入精准流量、温度基本恒定的冷却水来控制籽晶处的温度梯度，实现晶体高质量、高成品率的生长。

Description

一种可控温度梯度的晶体生长装置及方法 技术领域
本发明涉及半导体、光学晶体及金属晶体制备领域，尤其涉及使用垂直布里奇曼法及垂直梯度凝固法制备高成品率、低成本、低应力的晶体的装置和方法。
背景技术
用于半导体及光学晶体制备的主要的几种生长方法有：直拉法、垂直梯度凝固法(VGF)、垂直布里奇曼法(VB)等。
直拉法是较为传统的单晶制备方法，其特点是生长温度梯度高，晶体单晶成品率高，但此种方法制备的晶体应力大，位错等缺陷密度高，晶体易碎裂。垂直梯度凝固法和垂直布里奇曼法生长方法的特点是生长温度梯度低，制备的晶体温度梯度小。但由于生长时温度梯度过低，容易造成生长界面失稳，生长孪晶、多晶等晶体缺陷，导致降低晶体的成品率。此两种生长方法制备的晶体成本居高不下，尤其对于磷化铟、磷化镓、磷锗锌、锑化铟等易产生孪晶、多晶等缺陷或者易碎裂的晶体。
通常在晶体生长各项参数中，生长过程中的温度梯度对晶体的质量影响是最大的。结晶晶体中的温度梯度决定了晶体应力大小及位错密度的高低，晶体中温度梯度越大，晶体应力越大，位错密度也越高；熔体中的温度梯度决定了晶体生长界面是否失稳，尤其对于长尺寸化合物材料以及含有掺杂剂的单质材料来说影响很大，熔体中的温度梯度小，容易因固液界面前沿的组分偏离而造成成分过冷，从而导致界面失稳以及孪晶和多晶的出现。
传统控制温度梯度的方式是在坩埚外部设置分段加热器，每一段可以独立控制加热温度。但熔体的流动性在高温条件下非常好，这就导致了它的均匀性就非常好，尤其在保温条件比较好的装置中，热对流导致温度的均匀性很容易保持。对于坩埚比较深的情况，还会有非常多的涡流，涡流可能是旋转的，也可能在大的方向循环，温度梯度很难建立。
发明内容
本发明的目的是为了解决垂直梯度凝固法(VGF)、垂直布里奇曼法(VB)长晶低成品率问题。
为实现上述目的，本发明采用以下技术方案：
一种可控温度梯度的晶体生长装置，包括坩埚、坩埚托、坩埚杆、坩埚外围的加热器Ⅰ、加热器Ⅱ、加热器Ⅲ及配套的热偶，坩埚底部设置籽晶槽，关键在于，所述生长装置还包括熔体温度梯度控制机构、晶体温度梯度控制机构。
所述熔体温度梯度控制机构设置在坩埚内部，包括升降杆。、连接升降杆。的加热板，加热板内置发热丝和热偶Ⅳ。
所述晶体温度梯度控制机构包括恒温冷水机、连接恒温冷水机的冷水循环管路，所述冷水循环管路接近籽晶槽底部。
进一步地，所述加热板呈向下凹的弧面。
进一步地，所述冷水循环管路包括连接恒温冷水机的出水管、回水管，所述坩埚杆为中空管，所述出水管进入坩埚杆并延伸到坩埚杆的顶部，所述回水管连通坩埚杆和恒温冷水机。
在上述装置基础上，本发明还提出了一种可控温度梯度的晶体生长方法，所述生长方法包括以下步骤：
步骤1、使用去离子水对材料进行清洗，确保材料表面无污染；
步骤2、将籽晶放入坩埚底部的籽晶槽内；
步骤3、将熔体温度梯度控制机构下降至坩埚底部；
步骤4、将材料装入坩埚；
步骤5、开启恒温冷水机，冷水机流量设定为10L/min；
步骤6、开启加热器Ⅰ、加热器Ⅱ、加热器Ⅲ，设置温度分别高于材料熔点30℃、20℃、10℃；
步骤7、开启发热丝，使得热偶Ⅳ达到材料熔点温度以上3-15℃；
步骤8、恒温30-60min，确保坩埚的材料全部熔化；
步骤9、降低加热器Ⅰ、加热器Ⅱ、加热器Ⅲ的功率，设置温度分别高于材料熔点20℃，10℃，5℃；
步骤10、逐渐增加恒温冷水机供水流量，直至增加至30L/min，水流量增加速度为0.1L/min；
步骤11、上升熔体温度梯度控制机构，提拉速度为2-5mm/h；设置加热器Ⅰ、加热器Ⅱ、加热器Ⅲ的降温速率为1-3℃/h；
步骤12、熔体温度梯度控制机构离开熔体，晶体生长结束；
步骤13、加热器Ⅰ、加热器Ⅱ、加热器Ⅲ降温，降温速度100℃/h，完成晶体降温。
进一步地，步骤11中，加热板与固液界面的距离保持在5-15mm。
本发明，在装置中增加了熔体温度梯度控制机构和晶体温度梯度控制机构，通过精准控制，达到发明目的。
有益效果：本发明在熔体中设置可移动的加热装置，通过精准控制加热装置的位置 和温度来改善熔体中的温度梯度，使晶体生长界面稳定，减小孪晶和多晶出现的概率；在坩埚杆内部通入精准流量、温度基本恒定的冷却水，并且可以通过调节水流量来控制籽晶处的温度梯度。通过熔体中和籽晶处的温度梯度的精确控制实现晶体高质量、高成品率的生长。
附图说明
图1为装料完成后的装置组成图，
图2为材料完全融化后的装置状态图，
图3为晶体生长过程中的装置状态图，
图4为熔体温度梯度控制机构的示意图，
图5为本发明与传统方法合成磷化铟时固液界面前沿温度梯度曲线对比。
其中：1为热偶I，2为热偶Ⅱ，3为热偶ⅡI，4为加热器Ⅰ，5为加热器Ⅱ，6为加热器Ⅲ，7为坩埚，8为籽晶槽，9为材料，10为籽晶，11为回水管，12为坩埚杆，13为冷却水，14为出水管，15为热偶Ⅳ，16为升降杆，17为发热丝，18为恒温冷水机，19为生长的晶体，20为坩埚托。
具体实施方式
一种可控温度梯度的晶体生长装置，参看图1，包括坩埚7、坩埚托20、坩埚杆12、坩埚外围的加热器Ⅰ4、加热器Ⅱ5、加热器Ⅲ6及配套的热偶Ⅰ1、热偶Ⅱ2、热偶Ⅲ3；坩埚7底部设置籽晶槽8。
加热器和热偶为耦合控制对，通过热偶测试温度调节相应加热器的功率。
坩埚7采用石英、氮化硼等材料制作，用于放置籽晶、晶体、熔体及覆盖剂。
坩埚托采用氧化铝保温棉、碳毡等材料制作，对坩埚底部及籽晶起到保温作用。
生长装置还包括熔体温度梯度控制机构、晶体温度梯度控制机构。
熔体温度梯度控制机构设置在坩埚7内部，包括升降杆16、连接升降杆16的加热板，采用石英或氮化硼材料；加热板内置发热丝17和热偶Ⅳ15，如图4所示。
加热板从下面看为圆形，如图4所示，直径接近坩埚7的内径；加热板呈向下凹的弧面，形状与预想的晶体固液界面形状相仿。
发热丝17与热偶Ⅳ15为耦合控制对，通过热偶测试温度调节相应加热丝的功率，使得热偶处达到预设温度。升降杆16连接驱动装置(图中未表示)，使加热板可上下移动，速度1-50mm/h，速度可调。
晶体温度梯度控制机构包括恒温冷水机18、连接恒温冷水机18的冷水循环管路，所述冷水循环管路接近籽晶槽8底部，距离为3-10mm。
恒温冷水机18提供14-17℃的冷水，水温控制精度±0.5℃，最大水流量100L/min，流量由10-100L/min范围可调，流量控制精度±0.1L/min。
冷水循环管路包括连接恒温冷水机18的出水管14、回水管11，所述坩埚杆12作为冷水循环管路的一部分，为中空管，出水管14进入坩埚杆12并延伸到坩埚杆12的顶部，所述回水管11连通坩埚杆12和恒温冷水机18。
工作过程中，冷却水13从恒温冷水机18泵出，经出水管14进入坩埚杆12内部到达坩埚杆12的顶部，然后从坩埚杆12和出水管14中间位置，经回水管11流进恒温冷水机18。
出水管14、回水管11使用不锈钢材料，由保温材料包覆，管内直径10-20mm。
坩埚杆12中空部分的顶端距籽晶槽8的距离为3-10mm。
基于上述装置，本发明还提出了一种可控温度梯度的晶体生长方法，所述生长方法包括以下步骤：
步骤1、使用去离子水对材料9进行清洗，确保材料9表面无污染。
这里的材料9为半导体化合物，如磷化铟、磷化镓、磷锗锌、锑化铟等。
步骤2、将籽晶10放入坩埚底部的籽晶槽8内。
步骤3、通过驱动装置驱动升降杆16，将熔体温度梯度控制机构下降至坩埚7底部。
步骤4、将材料9装入坩埚7。
步骤5、开启恒温冷水机18，冷水机流量设定为10L/min。
此时装置的状态如图1所示。
步骤6、开启加热器Ⅰ4、加热器Ⅱ5、加热器Ⅲ6，设置温度分别高于材料9熔点30℃、20℃、10℃。
步骤7、开启发热丝17，使得热偶Ⅳ15达到材料9熔点温度以上3-15℃。
步骤8、待热偶Ⅰ1、热偶Ⅱ2、热偶Ⅲ3显示温度分别达到设定温度，恒温30-60min，确保坩埚7内的材料9全部熔化。
此时装置的状态如图2所示。
步骤9、降低加热器Ⅰ4、加热器Ⅱ5、加热器Ⅲ6的功率，设置温度分别高于材料9熔点20℃，10℃，5℃，此时依然可以确保熔体保持熔融状态。
步骤10、逐渐增加恒温冷水机供水流量，直至增加至30L/min，水流量增加速度为0.1L/min，满足结晶潜热释放要求。
此时接近籽晶10处的熔体9开始依附籽晶10按籽晶晶格排列凝固。
步骤11、上升熔体温度梯度控制机构，提拉速度为2-5mm/h。设置加热器Ⅰ4、加热器Ⅱ5、加热器Ⅲ6的降温速率为1-3℃/h，使得熔体逐渐凝固。
提拉速度一定程度上决定了晶体19的生长速度，并且能够提高固液界面前沿熔体中的温度梯度，确保界面前沿熔体厚度处于较低的值(一般要求温度梯度控制机构与固液界面距离为5-15mm)，从而保证晶体生长的稳定性。熔体中的温度梯度可以轻易的控制和获得数据，温度梯度＝(控制单元热偶温度-材料熔点)/固液界面和温度梯度控制单元的间距。传统方法中温度梯度的控制方法，加热器处于坩埚外，熔体的温度梯度较难控制和获得实际的梯度数据。
固液界面指晶体19(固体)上表面与熔体的接触面，是晶体生长的界面。
在晶体19生长过程中，在提拉的同时，保证加热板与固液界面的距离保持在5-15mm。
在现有的晶体生长技术中，尤其对于比较深的熔体的情况，由于熔体各处的温度差异、成分差异而常造成较为强烈的湍流，湍流可能是旋转的，可能是在整个熔体中循环。湍流的存在导致温度梯度的控制难以实现。并且处于远端的控制温度梯度的加热器，往往是隔着气氛和坩埚对熔体进行加热和控制的，控制过程不够直接，控制效果差。加之较深熔体中的复杂对流，梯度控制就更难了。此外，现有生长技术中，随着晶体生长的进行，固液界面逐步向熔体方向推进，周边固定的加热器对其影响效果也随之变化，温度梯度控制效果拥有较大的不确定性。
本实施例中，加热板与固液界面之间是很窄的夹缝，在空间上限制了湍流的范围，且温度控制单元距离生长界面较近，对固液界面的控制能力非常强，因此温度梯度比现有技术更容易保持和控制。并且，在固液界面向熔体推进的过程中，能够保持固液界面和温度控制单元的间距不变，从而保证整个晶体生长期间的温度梯度控制效果稳定。同时，在晶体生长过程中，坩埚外部的加热器与加热板的上升同步降温(1-3℃/h)，也保证了温度梯度的控制。
参看图5，以合成磷化铟为例，固液界面(横坐标为0的位置)的温度是磷化铟的熔点(1062℃)。采用传统方法，假设也在同样位置、同样温度进行加热，由于加热器设置在在坩埚外部，不同位置的温度变化不大，温度梯度不明显；采用本发明的装置和方法，在加热板和固液界面之间(本实施例中，加热板距固液界面9mm，温度设置为11℃)建立了基本上是线性的温度梯度。
图中，采用传统方法的曲线是理想情况：外部加热器的处在固液界面位置，实际操 作中，外部加热器一般是几个，且处于固定位置，很难在晶体生长全过程中实现精确位置控制。
外部加热器如果是在固液界面下方，提高加热器温度会同时加热晶体，造成晶体回化；如果在固液界面上方，则很容易因浮力对流(热的熔体密度低，自然上浮)而增加熔体的搅拌作用，使得温度场紊乱，难以建立梯度；如果在熔体上方，则往往因为隔得太远而不易控制温度，并且，熔体上方往往是气氛空间，通过气氛加热熔体是很难的。
此时装置的状态如图3所示。
步骤12、熔体温度梯度控制机构离开熔体，熔体也完全凝固，晶体生长结束。
步骤13、加热器I4、加热器II5、加热器III6降温，降温速度100℃/h，完成晶体降温。
降温后取出晶体19。
对于易挥发的材料，如磷化铟，在步骤4中，可装入密度低于材料且不沾污材料的覆盖剂，一般使用氧化硼(图中未标明)。
使用本发明方法进行SI型磷化铟晶体生长，较为明显的提高了晶体的成品率，并且所生长的晶体具有较低的应力和位错缺陷，对于提升晶体成品率具有非常好的效果，具体对比情况如下表所示。
方法 4英寸成品率 位错密度
传统VGF法 22.1％ ≤5000/cm 2
传统VB法 24.6％ ≤5000/cm 2
本发明应用于VGF法 33.2％ ≤5000/cm 2
本发明应用于VB法 38.0％ ≤5000/cm 2

Claims (9)

  1. 一种可控温度梯度的晶体生长装置，包括坩埚(7)、坩埚托(20)、坩埚杆(12)、坩埚外围的加热器Ⅰ(4)、加热器Ⅱ(5)、加热器Ⅲ(6)及配套的热偶，坩埚(7)底部设置籽晶槽(8)，其特征在于，所述生长装置还包括熔体温度梯度控制机构、晶体温度梯度控制机构；
    所述熔体温度梯度控制机构设置在坩埚(7)内部，包括升降杆(16)、连接升降杆(16)的加热板，加热板内置发热丝(17)和热偶Ⅳ(15)；
    所述晶体温度梯度控制机构包括恒温冷水机(18)、连接恒温冷水机(18)的冷水循环管路，所述冷水循环管路接近籽晶槽(8)底部。
  2. 根据权利要求1所述的可控温度梯度的晶体生长装置，其特征在于，所述加热板呈向下凹的弧面。
  3. 根据权利要求1所述的可控温度梯度的晶体生长装置，其特征在于，所述冷水循环管路包括连接恒温冷水机(18)的出水管(14)、回水管(11)，所述坩埚杆(12)为中空管，所述出水管(14)进入坩埚杆(12)并延伸到坩埚杆(12)的顶部，所述回水管(11)连通坩埚杆(12)和恒温冷水机(18)。
  4. 根据权利要求3所述的可控温度梯度的晶体生长装置，其特征在于，恒温冷水机(18)提供14-17℃的冷水，水温控制精度±0.5℃，最大水流量100L/min，流量由10-100L/min范围可调，流量控制精度±0.1L/min。
  5. 根据权利要求3所述的可控温度梯度的晶体生长装置，其特征在于，所述出水管(14)、回水管(11)使用不锈钢材料，由保温材料包覆，管内直径10-20mm。
  6. 根据权利要求3所述的可控温度梯度的晶体生长装置，其特征在于，所述坩埚杆(12)中空部分的顶端距籽晶槽(8)的距离为3-10mm。
  7. 一种可控温度梯度的晶体生长方法，基于权利要求1-6任一所述的可控温度梯度的晶体生长装置实现，其特征在于，所述生长方法包括以下步骤：
    步骤1、使用去离子水对材料(9)进行清洗，确保材料(9)表面无污染；
    步骤2、将籽晶(10)放入坩埚底部的籽晶槽(8)内；
    步骤3、将熔体温度梯度控制机构下降至坩埚(7)底部；
    步骤4、将材料(9)装入坩埚(7)；
    步骤5、开启恒温冷水机(18)，冷水机流量设定为10L/min；
    步骤6、开启加热器Ⅰ(4)、加热器Ⅱ(5)、加热器Ⅲ(6)，设置温度分别高于材料(9)熔点30℃、20℃、10℃；
    步骤7、开启发热丝(17)，使得热偶Ⅳ(15)达到材料(9)熔点温度以上3-15℃；
    步骤8、恒温30-60min，确保坩埚(7)内的材料(9)全部熔化；
    步骤9、降低加热器Ⅰ(4)、加热器Ⅱ(5)、加热器Ⅲ(6)的功率，设置温度分别高于材料(9)熔点20℃，10℃，5℃；
    步骤10、逐渐增加恒温冷水机供水流量，直至增加至30L/min，水流量增加速度为0.1L/min；
    步骤11、上升熔体温度梯度控制机构，提拉速度为2-5mm/h；设置加热器Ⅰ(4)、加热器Ⅱ(5)、加热器Ⅲ(6)的降温速率为1-3℃/h；
    步骤12、熔体温度梯度控制机构离开熔体，晶体生长结束；
    步骤13、加热器Ⅰ(4)、加热器Ⅱ(5)、加热器Ⅲ(6)降温，降温速度100℃/h，完成晶体降温。
  8. 根据权利要求7所述的可控温度梯度的晶体生长方法，其特征在于，
    步骤11中，加热板与固液界面的距离保持在5-15mm。
  9. 根据权利要求7所述的可控温度梯度的晶体生长方法，其特征在于，
    步骤4、将材料(9)和覆盖剂装入坩埚(7)。
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06157185A (ja) * 1992-09-25 1994-06-03 Furukawa Electric Co Ltd:The 化合物半導体単結晶の成長方法
CN206204482U (zh) * 2016-10-25 2017-05-31 珠海鼎泰芯源晶体有限公司 一种基于VGF法的减少InP晶体孪晶的装置
CN110042461A (zh) * 2019-04-30 2019-07-23 哈尔滨工业大学 一种增加热传递大尺寸磷化锗锌晶体的生长方法
CN114686963A (zh) * 2022-03-16 2022-07-01 北京通美晶体技术股份有限公司 一种GaAs单晶生长设备及GaAs单晶生长工艺
CN115216831A (zh) * 2022-07-15 2022-10-21 中国电子科技集团公司第十三研究所 一种可控温度梯度的晶体生长装置及方法

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0798717B2 (ja) * 1989-08-24 1995-10-25 科学技術庁無機材質研究所長 液面温度制御型の単結晶育成方法とその装置
JPH05194073A (ja) * 1991-06-07 1993-08-03 Furukawa Electric Co Ltd:The 化合物半導体の単結晶成長方法
JP2850581B2 (ja) * 1991-07-18 1999-01-27 日立電線株式会社 半導体結晶の製造方法およびその装置
JPH0881298A (ja) * 1994-09-16 1996-03-26 Furukawa Electric Co Ltd:The 単結晶製造方法および単結晶製造装置
JP2005132676A (ja) * 2003-10-30 2005-05-26 Canon Inc 単結晶製造方法及び装置
JP2005231978A (ja) * 2004-02-23 2005-09-02 Canon Inc 単結晶製造方法及び装置
DE602005027597D1 (de) * 2004-11-16 2011-06-01 Nippon Telegraph & Telephone Vorrichtung zur herstellung von kristall
JP2009149452A (ja) * 2007-12-18 2009-07-09 Hitachi Cable Ltd 半導体結晶成長方法
JP2011195375A (ja) * 2010-03-19 2011-10-06 Fuji Electric Co Ltd 単結晶成長方法および装置
CN102766901B (zh) * 2012-08-20 2015-09-30 元亮科技有限公司 实时可调温度梯度法生长大尺寸高温晶体的装置及方法
JP6969230B2 (ja) * 2017-08-30 2021-11-24 住友金属鉱山株式会社 単結晶育成方法及び単結晶育成装置
CN110195254B (zh) * 2019-07-12 2022-08-12 中国电子科技集团公司第二十六研究所 一种适用于提拉法的线圈可移动式温场结构与单晶生长方法
CN112746312B (zh) * 2021-02-03 2021-12-07 中国电子科技集团公司第十三研究所 一种低应力晶体的生长方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06157185A (ja) * 1992-09-25 1994-06-03 Furukawa Electric Co Ltd:The 化合物半導体単結晶の成長方法
CN206204482U (zh) * 2016-10-25 2017-05-31 珠海鼎泰芯源晶体有限公司 一种基于VGF法的减少InP晶体孪晶的装置
CN110042461A (zh) * 2019-04-30 2019-07-23 哈尔滨工业大学 一种增加热传递大尺寸磷化锗锌晶体的生长方法
CN114686963A (zh) * 2022-03-16 2022-07-01 北京通美晶体技术股份有限公司 一种GaAs单晶生长设备及GaAs单晶生长工艺
CN115216831A (zh) * 2022-07-15 2022-10-21 中国电子科技集团公司第十三研究所 一种可控温度梯度的晶体生长装置及方法

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