阅读说明：本技术 一种vgf法生长磷化铟单晶的方法 (Method for growing indium phosphide single crystal by VGF method ) 是由 包文瑧 柳廷龙 赵兴凯 普世坤 何永彬 叶晓达 祝永成 权忠朝 于 2021-07-15 设计创作，主要内容包括：本发明属于磷化铟单晶制备领域,具体公开一种VGF法生长磷化铟单晶的方法,包括以下步骤：采用VGF法,将原料放入坩埚内并组装单晶生长炉,进行高温退火处理；升温熔料,在加热控制程序中设置加热目标值进行加热和加压；熔种生长,设置生长温度,待籽晶熔融长度达到10-15mm,进行转肩生长时,坩埚位置开始下降,下降速度不大于2.5mm/h,生长结束后自动停止埚位下降；降温退火,生长结束后自动进入降温退火,温度降至350°后排空炉内气压,待炉内温度降至约150°后打开炉门,获取单晶,本发明增加了拉速方法,使得磷化铟单晶在生长过程中的热场更均匀,垂直定向结晶更平稳,生长出的磷化铟单晶更多,晶体合格率更高。(The invention belongs to the field of indium phosphide single crystal preparation, and particularly discloses a method for growing an indium phosphide single crystal by a VGF (vacuum gradient freeze) method, which comprises the following steps: putting the raw materials into a crucible by adopting a VGF method, assembling a single crystal growth furnace, and carrying out high-temperature annealing treatment; heating the melt, setting a heating target value in a heating control program for heating and pressurizing; the seed melting growth is carried out, the growth temperature is set, when the melting length of the seed crystal reaches 10-15mm, the crucible position starts to descend at the speed of not more than 2.5mm/h when the shoulder rotating growth is carried out, and the crucible position descending is automatically stopped after the growth is finished; and (3) cooling annealing, wherein the temperature is automatically reduced after the growth is finished, the air pressure in the furnace is exhausted after the temperature is reduced to 350 ℃, and the furnace door is opened after the temperature in the furnace is reduced to about 150 ℃ to obtain the single crystal.)

1. A method for growing indium phosphide single crystal by a VGF method is characterized by comprising the following steps:

s1: putting the raw materials into a crucible by adopting a VGF method, assembling a single crystal growth furnace, and vacuumizing, wherein the vacuum value is less than minus 1 Mp;

s2: heating the material, setting a heating target value in a heating control program for heating, filling inert gas from the bottom of the furnace chamber when the temperature reaches 350 ℃, stopping gas inlet when the pressure reaches 1.9Mpa, and when the temperature reaches the target value and a control curve is observed to be stable for 2 hours, increasing the pressure in the furnace to 2.8Mpa along with the temperature;

s3: setting a target value of a temperature zone, closing air inlet after the temperature rise is adjusted to reach the target value of the temperature zone, starting to descend the crucible when the melting length of the seed crystal reaches 10-15mm and the shoulder-rotating growth is carried out, wherein the descending speed is not more than 2.5mm/h, and automatically stopping the crucible descending after the growth is finished;

s4: and (4) cooling annealing, wherein the temperature is automatically reduced after the growth is finished, the air pressure in the furnace is exhausted after the temperature is reduced to 350 ℃, and the furnace door is opened after the temperature in the furnace is reduced to about 150 ℃ to obtain the single crystal.

2. The VGF method of growing an indium phosphide single crystal as claimed in claim 1, wherein the raw materials in step S1 include seed crystal, boron trioxide, high purity red phosphorus, dopant, polycrystalline material, the water content of said boron trioxide is less than 200PPm, the purity of said high purity red phosphorus and dopant is not less than 5N, and the mobility of said polycrystalline material is greater than 2000Cm 2/V.S.

3. The method of claim 2, wherein the dopant in step S1 is indium trisulfide or high purity iron.

4. The method of growing an indium phosphide single crystal by the VGF method as set forth in claim 1, wherein the target value in the step S2 or S3 is 1030 ℃ to 1080 ℃.

5. The method of claim 1, wherein the pulling rate growth rate in step S3 is 1.5mm/h, 1.6mm/h, 1.7mm/h, 1.8mm/h, 1.9mm/h, or 2 mm/h.

6. The VGF method for growing an indium phosphide single crystal as set forth in any one of claims 1 to 5, wherein the single crystal growth furnace in the step S1 comprises a hearth, a PBN crucible disposed in the hearth, a core for supporting the PBN crucible disposed at the bottom, and a heating layer and a plurality of thermocouples disposed between the PBN crucible and the hearth, wherein a pulling rate device is disposed between the bottom of the core and the bottom of the hearth, the pulling rate device comprises a pulling rate tray, a connecting rod, a fixed frame, the pulling rate tray is fixedly connected with the core, the connecting rod is an integrated single-shaft electrohydraulic connecting rod, the fixed frame is fixedly connected with the bottom, one end of the connecting rod is connected with the fixed frame, and the other end of the connecting rod is connected with the pulling rate tray.

7. The VGF method for growing an indium phosphide single crystal as claimed in claim 6, wherein the heating layer is divided into four heating zones on average, an independent thermocouple is arranged on each heating zone to form a temperature control thermocouple group, the first thermocouple, the second thermocouple, the third thermocouple and the fourth thermocouple are respectively arranged on the bottom side, the shoulder-laying position and the shoulder-rotating position of the seed crystal section of the PBN crucible, the fifth thermocouple, the sixth thermocouple and the seventh thermocouple are respectively arranged on the bottom side, the shoulder-laying position and the shoulder-rotating position of the seed crystal section of the PBN crucible, and four thermocouples bundled in parallel are further arranged between the heating layer and the PBN crucible to form a temperature measurement thermocouple group.

Technical Field

The invention belongs to the field of indium phosphide single crystal preparation, and particularly relates to a method for growing an indium phosphide single crystal by a VGF (vacuum gradient freeze) method.

Background

The indium phosphide single crystal is an important second-generation compound III-V semiconductor crystal after germanium crystal and gallium arsenide crystal, is mainly used in the fields of photoelectron technology, microwave technology, space satellite communication and the like, and has higher requirements on the preparation process of high-quality indium phosphide single crystal materials applied in the field of high-power microwave. The indium phosphide single crystal whisker can be prepared only at high temperature and high pressure, and the stacking fault energy of indium phosphide is low, twin crystals are easily generated, so that the indium phosphide single crystal with large size and high quality is difficult to prepare. The yield of the indium phosphide single crystal grown by the VGF is lower than that of the indium phosphide single crystal grown by the LEC method, but the dislocation is low, and the electrical property parameters are uniformly distributed, so that the high-quality indium phosphide single crystal is usually obtained by the VGF growth.

In the application aspect: with the continuous improvement of satellite communication technology, indium phosphide single crystals grow explosively in the 5G application market, so that high-quality and large-size (4 '-6') indium phosphide single crystals are applied to high-power microwave devices and have a mainstream development trend. And the indium phosphide single crystal obtained by the traditional VGF growth has low qualification rate, mainly takes 2 'and a small amount of 3' as main diameters, and is difficult to meet the requirements of application markets. Although the crystallization rate of the indium phosphide single crystal grown by LEC is high, the application life and the cost of the high-power microwave device are indirectly influenced by high dislocation and uneven carrier concentration and electron mobility distribution. Tables 1 and 2 below show the description of LEC-grown indium phosphide single crystals and conventional VGF-grown indium phosphide single crystals,

based on the result that the LEC and the traditional VGF adopt different process conditions to grow the indium phosphide single crystal in different environments, the process method is based on the improvement of the crystallization rate of the VGF crystal and the control of lower crystal dislocation and better uniformity of carrier concentration and electron mobility, thereby improving the growth efficiency and quality of the crystal and reducing the production cost.

Disclosure of Invention

The invention mainly aims to provide a method for growing an indium phosphide single crystal by a VGF (vacuum vapor deposition) method, which aims to solve the problem that the growth percent of the indium phosphide single crystal is low because the dissociation pressure of the indium phosphide crystal is 2.75MPa, the single crystal growth is required to be finished under the pressure of 2.75MPa, and the growth thermal field is a high-pressure closed thermal field which can only obtain the indium phosphide single crystal by cooling growth.

In order to achieve the above purpose, the invention provides the following technical scheme:

a method for growing an indium phosphide single crystal by a VGF method comprises the following steps:

s1: putting the raw materials into a crucible by adopting a VGF method, assembling a single crystal growth furnace, and vacuumizing, wherein the vacuum value is less than minus 1 Mp;

s2: heating the material, setting a heating target value in a heating control program for heating, filling inert gas from the bottom of the furnace chamber when the temperature reaches 350 ℃, stopping gas inlet when the pressure reaches 1.9Mpa, and when the temperature reaches the target value and a control curve is observed to be stable for 2 hours, increasing the pressure in the furnace to 2.8Mpa along with the temperature;

s3: setting a target value of a temperature zone, closing air inlet after the temperature rise is adjusted to reach the target value of the temperature zone, starting to descend the crucible when the melting length of the seed crystal reaches 10-15mm and the shoulder-rotating growth is carried out, wherein the descending speed is not more than 2.5mm/h, and automatically stopping the crucible descending after the growth is finished;

s4: and (4) cooling annealing, wherein the temperature is automatically reduced after the growth is finished, the air pressure in the furnace is exhausted after the temperature is reduced to 350 ℃, and the furnace door is opened after the temperature in the furnace is reduced to about 150 ℃ to obtain the single crystal.

The raw materials in the step S1 comprise seed crystals, boron trioxide, high-purity red phosphorus, a doping agent and a polycrystalline material, wherein the water content of the boron trioxide is less than 200PPm, the purities of the high-purity red phosphorus and the doping agent are not less than 5N, and the mobility of the polycrystalline material is more than 2000Cm 2/V.S.

The dopant in step S1 is indium trisulfide or high purity iron.

The target value in the step S2 or S3 is 1030 ℃ to 1080 ℃.

The pulling rate growth speed in the step S3 is 1.5mm/h, 1.6mm/h, 1.7mm/h, 1.8mm/h, 1.9mm/h and 1.9 mm/h.

The invention has the following beneficial effects:

1. the pulling speed method is added, so that the thermal field of the indium phosphide single crystal in the growth process is more uniform, the vertical directional crystallization is more stable, more indium phosphide single crystals grow, the dislocation, the electron mobility, the carrier concentration and the resistivity distribution ratio are more uniform, and the crystal qualification rate is higher.

2. The fixing mode of the temperature control thermocouple and the temperature measurement thermocouple in the furnace preparation link in the process of preparing the indium phosphide single crystal (VGF) is changed, and the temperature measurement is more accurate and more stable than the traditional temperature measurement.

3. The automatic temperature control and temperature regulation functions are added, so that the temperature control is more accurate, and the temperature stability is improved.

Drawings

FIG. 1 is a diagram showing the metallographic microscope result of a head piece with a crucible position falling speed of 0 mm/h;

FIG. 2 is a diagram showing the metallographic microscope result of a head piece with the crucible position falling speed of 1.5 mm/h;

FIG. 3 is a diagram showing the metallographic microscope result of a head piece with a crucible position falling speed of 2.5 mm/h;

FIG. 4 is a structural view of a single crystal growing furnace according to the present invention;

wherein: 1. a hearth; 2. a power line; 3. a connecting wire; 4. an inert gas charging port; 5. a barometer; 6. a heating layer; 7. a quartz hearth tube; 8. a quartz material pipe; 9. sealing a cap by quartz; 10. a PBN crucible; 11. a quartz outer support tube; 12. a quartz inner supporting tube; 13. wet cotton; 14. a quartz rod; 15. pulling a tray; 16. a connecting rod; 17. a fifth thermocouple; 18. a sixth thermocouple; 19. a seventh thermocouple; 20. a temperature thermocouple group; 21. a first thermocouple; 22. a second thermocouple; 23. a third thermocouple; 24. a fourth thermocouple; 25. a fixing frame.

Detailed Description

The invention is further described with reference to the following figures and specific examples.

Example 1

The process for growing the indium phosphide single crystal comprises the following steps: preparing materials → preparing furnace → charging → raising temperature melting → melting seeds → growing → cooling annealing → discharging from furnace and demoulding;

1. preparing materials: under hundred-grade environment, seed crystal, boron trioxide (the water content is less than 200 PPm), high-purity red phosphorus (5N), dopant (indium trisulfide of 5N or high-purity iron of 5N) and polycrystalline material (the mobility is more than 2000Cm2/V.S) are put into a cleaned PBN crucible, a quartz sealing cap is covered, a quartz tube is put into the crucible, the crucible is vacuumized, and then oxyhydrogen flame sealing welding is carried out for standby. Note: the PBN crucible is annealed by introducing oxygen at a high temperature (1200 ℃).

2. The furnace preparation is specifically shown in figure 4:

2.1 a quartz tube 8, a quartz hearth tube 7, a heating layer 6 and other conventional structures are sequentially arranged between the PBN crucible 10 and the high-pressure furnace chamber 1, and then quartz sand is filled in the gap. The high-pressure furnace chamber 1 is conventionally arranged in the prior art and is made of cylindrical stainless steel, an upper furnace door and a lower furnace door are respectively provided with a sealing rubber strip as a high-pressure sealing element, wherein the upper furnace door is provided with a pressure gauge, the lower furnace door is provided with a power supply connecting sealing element and a thermocouple connecting sealing element.

2.2 the furnace core part for supporting the PBN crucible is assembled by using the prior art, the quartz rod 14, the wet cotton 13, the quartz inner supporting tube 12, the wet cotton, the quartz outer supporting tube 11 and the wet cotton are arranged in sequence from inside to outside, the fifth thermocouple 17 and the sixth thermocouple 18 are fixed on the quartz rod 14, wrapped with the wet cotton 13 and plugged into the quartz inner supporting tube 12, then wrapped with the wet cotton and plugged into the quartz outer supporting tube 11, the seventh thermocouple 19 is fixed outside the quartz outer supporting tube 11 and wrapped with the wet cotton, finally the fifth thermocouple, the sixth thermocouple and the seventh thermocouple are arranged in the quartz tube 8, the temperature of the bottom side, the shoulder placing position and the shoulder rotating position of the PBN crucible seed crystal section is measured respectively, after the installation, the high-temperature baking is carried out, and the furnace core part is arranged at the bottom of the PBN crucible after the annealing and the cooling.

2.3 the heating layer 6 is divided into four heating zones equally, each heating zone is provided with an independent thermocouple to form a temperature control thermocouple group, which is a first thermocouple 21, a second thermocouple 22, a third thermocouple 23 and a fourth thermocouple 24, and the thermocouples are arranged and fixed on the heating layer 6 according to the size and position requirements. Furnace core bottom and furnace 1 bottom between be provided with the speed device of drawing, the speed device of drawing is including drawing fast tray 15, connecting rod 16, mount 25, the electronic hydraulic connecting rod of connecting rod formula unipolar as an organic whole, furnace core bottom and the speed tray 15 joint of drawing, and the quartz rod 14 at furnace core middle part passes and draws fast tray 15, scarf joint in the hollow position at 16 tops of unipolar hydraulic connecting rod, mount 25 and 1 bottom fixed connection of furnace, mount 25 top center opening, with connecting rod 16 scarf joint mutually, the electronic hydraulic connecting rod 16 power of integral type unipolar passes the furnace bottom cover through the sealing member and is connected with external power source.

4 thermocouples which are bundled in parallel and have the diameter of 0.8mm are also arranged at the gap between the quartz hearth pipe 7 and the heat preservation hearth piece 8 to form a temperature thermocouple group 20, the temperature thermocouple group 20 is four thermocouples with certain size and length requirements, and the temperature thermocouples are sequentially arranged at the gap between the quartz pipe 8 and the quartz hearth pipe 7 (the equal-diameter position after the crystal growth rotary shoulder is sequentially inserted, the 2/5 position with the total length of the equal diameter, the 1/2 position with the total length of the equal diameter and the tail part of the crystal) side by using an insulation cotton plug for fastening.

The heating layer is connected to a power control cabinet outside the furnace chamber through a power line 2, and the thermocouple also transmits signals to the outside through a connecting line 3.

2.4 after the whole device is assembled, punching the furnace chamber for detecting leakage, wherein the gas leakage rate is less than 0.1 Mpa/24H. The pressure change of the external barometer at the top of the furnace chamber can be observed and recorded.

2.5 the oven cavity and the support are leveled.

3. Charging: and vertically installing the packaged quartz material pipe on a furnace core bracket, filling heat preservation cotton in the heating layer and the hearth piece, checking the installation condition of a thermocouple, and then closing a furnace door.

4. Heating and melting: setting target values of temperature control thermocouples in a temperature control system, wherein the target values comprise a first thermocouple 21 (about 1030 degrees), a second thermocouple 22 (about 1040 degrees), a third thermocouple 23 (about 1070 degrees), a fourth thermocouple 24 (1080 degrees) and heating time (4-6 hours), starting a heating function, opening an air inlet valve to fill nitrogen into a high-pressure furnace chamber within 10-30 Min time till the furnace pressure is 1.9MPa after a fifth thermocouple 17 and a sixth thermocouple 18 reach 150 degrees and a temperature thermocouple group 20 reaches the maximum value of 350 degrees, and closing the air inlet valve.

And (3) keeping the temperature for 2 hours after the temperature control thermocouple group reaches a set target value, setting the target values (1020-1090 degrees) of seven thermocouples of the temperature measurement thermocouple group 20, the fifth thermocouple 17, the sixth thermocouple 18 and the seventh thermocouple 19 when the pressure in the furnace reaches 2.7-2.8Mpa along with the temperature rise, starting the temperature regulation function, and regulating the temperature of the temperature control thermocouple of the heating zone, so that the temperature difference of the temperature measurement thermocouple group 20, the fifth thermocouple 17, the sixth thermocouple 18 and the seventh thermocouple 19 is equally divided into temperature areas of 7 thermocouples and kept constant within a certain time, and the fluctuation of the temperature measurement point of each thermocouple is less than +/-1 degree.

5. And (3) molten seed growth: adjusting the temperature value of the temperature control thermocouple according to the temperature display value of the temperature control thermocouple, wherein the temperature zone target difference value is about: 50 degrees, low temperature zone 1030 degrees, high temperature zone 1080 degrees, close this moment and admit air, ensure that the air current in the high-pressure chamber is in relative quiescent condition, avoid undulant because of the thermal current (thermal field) that the air current arouses, wait that seed crystal melting length reaches 10-15mm, keep a certain time, when carrying out the shoulder of turning round growth, crucible position begins to descend, makes the steady slow decline of stove core frame that supports the crucible, its speed is 1.5mm/h, and the automatic shutdown crucible position descends after the growth finishes.

6. Cooling and annealing: and (4) automatically cooling and annealing after the growth is finished, and exhausting the air pressure in the furnace after the temperature is reduced to 350 ℃.

7. Discharging from the furnace and demoulding: and opening the furnace door after the temperature in the furnace is reduced to about 150 ℃, taking out the material pipe, crushing the quartz material pipe, taking out the PBN crucible containing the crystal, putting the PBN crucible into an ultrasonic cleaning machine, performing vibration cleaning on 3B2O between the crystal and the PBN crucible and red phosphorus on the surface of the PBN crucible, taking out after 8 hours, and demolding to obtain the indium phosphide single crystal.

And (3) comparing test results:

the process adopts the crucible position descending speed: 0mm/h, 1.0mm/h, 1.5mm/h, 1.8mm/h, 2.0mm/h, 2.5mm/h, respectively, 1 furnace 4' -indium phosphide single crystal (5Kg + -50 g) was grown, and the crystal dislocation, carrier concentration, electron mobility, crystal formation ratio were tested.

And (3) adopting a metallographic microscope 100 times lower (137 lattice) test method for crystal dislocation and carrying out single-point calculation. For the crystal carrier concentration and the electron mobility, a Hall 4 probe test method is adopted. The crystal forming ratio is calculated by using conventional measurement.

Respectively cutting the head and the tail of a crystal grown from a crucible position (0) to obtain a wafer with the thickness of 1mm, corroding and grinding by a chemical method, and observing dislocation by using a wafer dislocation recognition counter to obtain: the head mean dislocation was 100 and the tail mean dislocation was 1000, indicating that the crystal dislocation was less than 500. The results of the head-piece metallographic microscope are shown in FIG. 1.

The qualified length of the crystal grown at the crucible position falling speed of 1.5mm/h is as follows: cutting 3 inches and 15mm respectively head and tail to obtain chips with the thickness of 1mm, corroding and grinding by a chemical method, and observing dislocation by using a wafer dislocation recognition counter to obtain: the head 50 and tail 150 mean dislocations, indicating that the crystal dislocations are less than 100, and the head metallographic microscope results are shown in figure 2.

Respectively cutting the head and the tail of a crystal grown at the crucible descending speed of 2.5mm/h to obtain a chip with the thickness of 1mm, corroding and grinding by a chemical method, and observing dislocation by using a wafer dislocation recognition counter to obtain: the mean dislocation of the head piece was 1000 and the mean dislocation of the tail piece was 3000, indicating that the crystal dislocation was less than 3000. The results of the head-piece metallographic microscope are shown in FIG. 3.

The carrier concentration and electron mobility of a 1cm x 1cm sample wafer after dislocation detection were measured by a hall 4 probe and are shown in table 3:

summarizing the data in tables 3, 4, and 5, it can be seen that: more indium phosphide single crystals grow by increasing the crucible position reduction method (the pulling speed is 1.5-2 mm/h), the dislocation, the electron mobility, the carrier concentration and the resistivity distribution are more uniform than those under other 3 conditions, and the crystal qualification rate is higher.

The process method can accurately control the temperature control of each temperature zone on the temperature rising and melting stage, the seed crystal welding stage, the crystal growth stage and the crystal cooling and annealing stage in the single crystal growth process by improving the measuring positions of the high-pressure furnace chamber and the thermocouple, automatically adjusting the target value of the furnace body temperature zone, automatically controlling the crucible position to descend and correspondingly controlling the process. The stability and uniformity of parameters such as dislocation, carrier concentration, mobility, resistivity, thermal stress and the like are ensured on the premise of further improving the single crystal crystallization rate. The growing Inp single crystal with high qualification rate has a high thermal field to the thermal field, the longitudinal temperature gradient and the radial temperature gradient of the thermal field influence the longitudinal and radial solid-liquid segregation interface of the Inp single crystal during growth in the growth process of the Inp single crystal, and are influenced by the heat release of crystal crystallization and the heat convection of gradient heat supply of the thermal field in the relatively standing thermal field, so that the concavo-convex shape of the solid-liquid conversion interface in the growth process of the single crystal is caused, the concavo-convex shape of the solid-liquid interface directly influences the crystallization surface, dislocation, carrier concentration and electron mobility of the crystal, and the heating furnace wire of a heating element is annular heating and is influenced by the uniformity of the heat insulation layer, and the matching degree of the longitudinal and radial temperature gradients of the crystal growth directly determines the diameter of the crystal growth and the crystal forming rate of the crystal. After the crucible position reduction method is added, the heat convection in the solid-liquid interface conversion process during crystal growth is optimized, so that the solid-liquid interface conversion is more stable, and the flatness of the solid-liquid interface is increased. The uniformity of unit cell arrangement and the consistency of solid-liquid segregation are improved, the crystal forming rate of the crystal is guaranteed, dislocation is reduced, and the carrier concentration and the electron mobility are uniform. The pulling speed in the growth of the VGF method is horizontal and vertical downward pulling, the material pipe which is well loaded is placed in a heat preservation bracket (the furnace preparation process 2 is completed) in the process of the process implementation, the heat preservation bracket is independently and horizontally and vertically fixed on a pulling speed platform, and the material pipe in the heat preservation bracket also slowly descends along with the heat preservation bracket in the process of downward opening of the pulling speed, so that the process is different from the vertical upward pulling in the LEC method.

In order to guarantee the implementation of the pulling speed method, the invention carries out matching adjustment on the high-pressure cranial cavity structure, the heat-preservation hearth, the thermocouple measuring position, the thermocouple fixing method and the temperature adjusting mode.