CN102965734A - Rapid synthesis method of indium phosphide polycrystalline material and multi-tubular quartz phosphorus bubble thereof - Google Patents
Rapid synthesis method of indium phosphide polycrystalline material and multi-tubular quartz phosphorus bubble thereof Download PDFInfo
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Abstract
The invention discloses a rapid synthesis method of an indium phosphide polycrystalline material, which comprises the following steps of: (I) performing surface cleaning treatment on indium; (II) placing a multi-tubular quartz phosphorus bubble with phosphorus into a phosphorus source furnace; (III) placing the pre-designed thermal insulation system, heater, crucible with indium, phosphorus source furnace and seed crystal and B2O3 into a high-pressure single-crystal furnace hearth; (IV) vacuumizing the inside of the furnace and filling high-purity argon; (V) heating to vaporize phosphorus in the phosphorus bubble and injecting into indium melt, and reacting to generate indium phosphide; and (VI) growing crystal. The multi-tubular quartz phosphorus bubble comprises a quartz phosphorus container, at least two quartz phosphorus bubble tubes and a quartz cover. By adopting a multi-tubular quartz phosphorus bubble, the method disclosed by the invention realizes a rapid multi-tubular phosphorus injection synthesis technology, solves the problems of long synthesis time, non-uniform melt proportioning, impurity pollution and the like in the original technology, realizes rapid, efficient and high-purity synthesis of the indium phosphide material, and performs InP single crystal growth more easily.
Description
Technical field
The present invention relates to technical field of semiconductors, particularly the synthetic method of indium phosphide polycrystalline material.
Background technology
Indium phosphide (InP) is to form the III-V group iii v compound semiconductor material by III family element indium (In) and V group element phosphorus (P) chemical combination, having very important strategic status in field of semiconductor materials, is the irreplaceable semiconductor material of present photoelectric device and microelectronic device.Compare with germanium, silicon materials, InP has many advantages: direct transition type energy band structure has high electro-optical efficiency; Electronic mobility is high, is easy to make semi insulating material, is fit to make high frequency microwave device and circuit; Working temperature is high; Has strong capability of resistance to radiation; Efficiency of conversion as solar cell material is high.Therefore, the material such as InP is widely used in the high-tech sectors such as solid luminescent, micro-wave communication, opticfiber communication, microwave, millimetric wave device, radioprotective solar cell.
Progress along with energy band engineering theory, ultra-thin materials Technology and deep-submicron manufacturing technology, InP also more and more demonstrates its advantage aspect high-end microwave, millimeter wave electronic device and opto-electronic device, become the preferred material of the high-end device of millimeter wave, paid attention to widely, development prospect is boundless.Preparation, the especially preparation of major diameter high pressure LEC (liquid encapsulation Czochralski) (HP-LEC) InP monocrystalline of the high quality InP monocrystalline with good integrity, homogeneity and thermostability depended in the realization of high-end InP base microelectronics and opto-electronic device.High-purity, different melt proportioning, be the precondition of producing high quality InP and carrying out the research of InP correlation properties without the InP polycrystal that is mingled with.A lot of characteristics of InP crystal, all with starting raw material, namely the characteristic of polycrystalline material is relevant, such as the proportioning degree of material, the purity of material, to the crystal growth, the electricity performance of crystal, perfection of crystal, homogeneities etc. all have a great impact.Therefore, the fast high-capacity of InP melt is synthetic is the very concerned problem of InP research field.
At present, the problem of the method for several synthetic InP polycrystals commonly used and existence thereof is as follows:
(1) horizontal Bridgman method (HB) and horizontal gradient freezing method (HGF): adopt horizontal Bridgman method (HB) and horizontal gradient freezing method (HGF) to synthesize the InP material, on technique, the larger then generated time of resultant quantity is longer, general need about 24h with the synthetic 1.5KgInP polycrystalline of HB/HGF technology, so the contamination of Si also more obvious (its source is quartzy tube wall); The carrier concentration of the industrial InP polycrystalline that provides is minimum to be 6 * 10
15Cm
-3, for preparation high-performance microelectronic device and photoelectric device bad impact is arranged, and the possibility of " bombing " is also large.The synthetic boat of form whatsoever, the weight that increases In is all very difficult, and increases the diameter of silica tube, certainly will require more bigbore autoclave, and cost also will increase sharply.
(2) the direct synthetic technology of liquid phosphorus liquid encapsulation technique and ultra-high voltage: because the speed of the method synthesised polycrystalline is fast, purity is high; therefore also once there was the investigator that it is studied; but these class methods are too high to equipment requirements; and resultant quantity is less; can not large-scale production, still do not have at present practicality.
(3) synthetic method such as horizontal Bridgman method (HB) and horizontal gradient freezing method (HGF) and the direct synthetic technology of ultra-high voltage: these methods all are to carry out first InP to synthesize in synthetic furnace, then synthetic InP polycrystal is taken out from synthetic furnace, polycrystalline material is cleaned corrosion treatment, and then carry out the InP single crystal growing in the high pressure single crystal growing furnace of packing into.Synthetic " two steps " method that adopts with the crystal growth is carried out, and this has just increased the possibility that material is stain greatly, and has increased the material preparation cost.
In sum as can be known, best polycrystalline synthetic technology should have following characteristics concurrently: can generate highly purified polycrystalline, a small amount of as far as possible indium is remaining and resultant velocity faster, and can realize namely can carrying out continuously the crystal growth behind the synthesised polycrystalline.According to these characteristics, just require to carry out original position and synthesize.The liquid phosphorus liquid encapsulation technique can accomplish that original position is synthetic, and continuous crystal-pulling, but it uses liquid white phosphorus as insulating covering agent, causes the crystal growth can't direct viewing, and crystal forming rate is excessively low, does not possess practicality.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of fast synthesis method of indium phosphide polycrystalline material.The method adopts the quartzy phosphorus bubble of multitube to realize that quick multitube phosphorus injects synthetic technology, the problems such as generated time length, melt proportioning inequality and contaminating impurity in original synthetic technology have been solved, the rapidly and efficiently high purity that has realized indium phosphide is synthetic, and carries out the InP single crystal growing easilier.
For solving the problems of the technologies described above, the technical solution used in the present invention is:
A kind of fast synthesis method of indium phosphide polycrystalline material may further comprise the steps:
The first step is carried out surface cleaning processing to indium, with the indium dry for standby after cleaning;
Second step is packed the quartzy phosphorus bubble of multitube (such as 2,3,4,5,6 etc.) that phosphorus is housed in the phosphor source oven into, and the quartzy phosphorus bubble of multitube comprises at least two quartzy phosphorus bubble pipes;
The 3rd step, with high pressure single crystal growing furnace scrub, the heat-insulation system that then will design in advance, well heater, the crucible that indium is housed, synthetic used phosphor source oven and seed crystal and fluid-tight agent B
2O
3Put in the high pressure single crystal growing furnace burner hearth;
In the 4th step, to vacuumizing in the stove, then fill high-purity argon gas;
In the 5th step, phosphorus is steeped interior phosphorus heating vaporization be injected into reaction generation indium phosphide in the indium melt;
In the 6th step, carry out the crystal growth.
The first step is carried out surface treatment to remove oxide compound and the residual impurity on indium surface to indium, guarantee that indium reaches the 6N purity, and the surface is without dust impurity.
Second step, the purity of phosphorus are 6N.
Vacuum tightness in the 4th step in the stove is less than 10
2Pa.
Fill the high-purity argon gas of 2MPa in the 4th step in the stove.
The 5th step was heated to preset temperature with indium melt in the crucible, behind temperature-stable quartzy phosphorus bubble pipe was inserted in the indium melt, and the phosphorus heating vaporization in phosphorus is steeped is injected into reaction generation indium phosphide in the indium melt.Preset temperature is 1355～1395K.
Adopt high-pressure liquid encapsulation pulling method to carry out the crystal growth in the 6th step.
The quartzy phosphorus bubble of the special-purpose multitube of the fast synthesis method of indium phosphide polycrystalline material comprises the quartzy phosphorus container (1) for splendid attire solid phosphorus, at least two quartzy phosphorus bubble pipe (2) and quartz cover (3); Phosphorus bubble pipe (2) bottom is pierced in the phosphorus container from the bottom of quartzy phosphorus container (1), and phosphorus bubble pipe (2) bottom has the hole that phosphorus supply steam passes through, and the opening end of phosphorus bubble pipe (2) is positioned at outside the quartzy phosphorus container (1); Be tightly connected between phosphorus bubble pipe (2), quartz cover (3) and the quartzy phosphorus container (1).
The quartzy phosphorus bubble of the special-purpose multitube of the fast synthesis method of preferred indium phosphide polycrystalline material comprises two quartzy phosphorus bubble pipes (2).
The purity of high-purity argon gas is more than 99.999%.
Preset temperature in the 5th step refers to the indium melt is heated to above 20～60 ℃ of the fusing points (1062 ℃) of indium phosphide; When the bubble that bloats in the phosphorus bubble tails off or can increase the heating power of phosphor source oven during the liquid level non-jitter, power is controlled as shown in Figure 3.
The original position synthetic technology refers to that all manufacture crafts all are to carry out in the high pressure single crystal growing furnace.
The technical progress of adopting technique scheme to obtain is: the present invention adopts multitube phosphorus to inject synthetic technology synthetic InP melt in the high pressure single crystal growing furnace, this technology has overcome that the single tube generated time is long, phosphorous vapor easy fried shortcoming of steeping of skewness in bubble, adopt simultaneously the original position synthetic technology, have synthetic after continuously crystal growth, crystal synthesize the high advantage of purity, particular embodiment is as follows:
1, in the technological process, adopt the multitube synthetic technology, so that phosphorus steam and indium melt contact area strengthen, the bubble internal pressure is dredged easily, has substantially avoided the directly problem of synthetic easy fried bubble, has also solved the synthetic interior more problem of residual phosphorus amount of bubble that easily causes of large capacity, after reaction is finished, can residual 15～30g phosphorus in the general single tube phosphorus bubble, and the two-tube interior residual 5g that is lower than, in addition two-tube phosphorus bubble synthetic after transparent residual phosphorus amount＜3g almost in the bubble;
2, can realize that fast high-capacity is synthetic: adopts two-tube after under the identical condition of basic maintenance generated time, resultant quantity is brought up to 3～4Kg level by 1Kg;
3, the reaction contact area owing to phosphorus steam and indium melt increases, so that synthetic more steady, solved and easily caused melt proportioning problem of non-uniform in original indium phosphide synthesis technique;
4, the possibility that the material of having avoided used " two steps " method of additive method to cause is stain, and can accurately control the amount of In, P, the synthetic InP melt that obtains rich indium, nearly stoicheiometry and rich phosphorus can carry out the crystal growth under the condition of different melt stoichiometric ratio respectively.
Description of drawings
Fig. 1 is the structural representation of the quartzy phosphorus bubble of original single tube;
Fig. 2 is the structural representation of the two-tube quartzy phosphorus bubble of the present invention;
Fig. 3 is phosphor source oven intensification power temporal evolution rate diagram;
1 is quartzy phosphorus container, and 2 is quartzy phosphorus bubble pipe, and 3 is quartz cover.
Embodiment
The fast synthesis method of indium phosphide polycrystalline material synthesizes the nearly stoicheiometry InP of 3.0kg polycrystalline material, and concrete operation step is:
The first step, in order to remove the factors such as packing to raw-material contamination, with MOS level dilute hydrochloric acid indium is carried out the light corrosion in surface first, then repeatedly boil cleaning with deionized water, to remove oxide compound and the residual impurity on indium surface, guarantee to test used high purity indium and reach the 6N purity, and the surface is without impurity such as dust, indium after the cleaning is placed on and cures about 30min in the vacuum drying oven, and is for subsequent use;
Second step steeps the two-tube quartzy phosphorus that 6N phosphorus is housed in the phosphor source oven of packing into, and synthetic with two phosphorus bubbles, phosphor source oven adopts the molybdenum filament coiling, is quartzy round aecidioid;
The 3rd step, with high pressure single crystal growing furnace scrub, the heat-insulation system that then will design in advance, well heater, the crucible that indium is housed, synthetic used phosphor source oven and seed crystal and fluid-tight agent B
2O
3Put in the high pressure single crystal growing furnace burner hearth; The batch of starting material indium and phosphorus is respectively 2700g and 780g, dehydration boron oxide 400g;
Crucible is that diameter is round bottom or the flat crucible of 135mm;
The 4th step, close fire door, vacuumize with mechanical pump, after vacuum tightness reaches 60Pa, stop to vacuumize, fill the high-purity argon gas of 2MPa;
The 5th step, indium melt in the crucible is heated to 1375K, and behind temperature-stable, the phosphorus bubble is inserted in the indium melt, by observing bubble and the liquid level situation that bloats in the phosphorus bubble, the power of phosphor source oven heating is slowly increased, and the phosphorus heating vaporization in phosphorus is steeped is injected into reaction generation indium phosphide in the indium melt; Power heating curve in time as shown in Figure 3, always the synthetic time is 53 minutes;
The phosphorus bubble is inserted in the indium melt, and by progressively improving phosphor source oven power, power is controlled as shown in Figure 3, controls suitable phosphorus vapour pressure, makes phosphorus steam not too sharply enter melt, reduces the loss of phosphorus, and also bubbling is excessively unslow, prevents that the melt suck-back from causing fried bubble.Until a bubble synthetic complete after, mention and remove the phosphorus bubble.Melt temperature is suitably reduced, and then as above synthetic second phosphorus of method steeps.
The 6th step, after two phosphorus bubbles have synthesized, remove phosphor source oven, the decline seed crystal directly carries out the growth of liquid encapsulate Czochralski technique (LEC) crystal.
Two-tube quartzy phosphorus bubble comprises that the quartzy phosphorus container 1 for splendid attire solid phosphorus, two quartzy phosphorus steep pipe 2 and quartz cover 3; Phosphorus bubble pipe 2 bottoms are pierced in the described phosphorus container from the bottom of quartzy phosphorus container 1, and phosphorus bubble pipe 2 bottoms have the hole that phosphorus supply steam passes through, and the opening end of phosphorus bubble pipe 2 is positioned at outside the quartzy phosphorus container 1; Be tightly connected between phosphorus bubble pipe 2, quartz cover 3 and the quartzy phosphorus container 1.
The concrete technology condition is in the present embodiment: synthetic melt temperature: 1355～1395K, synthesis pressure: 3.5～4.5Mpa, crucible rotation: 10～15rpm.
Take high-purity red phosphorus P (6N) and high purity indium In (6N) as starting material, with dehydration boron oxide (B
2O
3) be the fluid-tight agent, adopt the purity of the synthetic nearly stoicheiometry InP polycrystalline of two-tube phosphorus method for implanting higher, its average carrier concentration is 2.72 * 10
15Cm
-3, average mobility is 4.45 * 10
3Cm
2/ V.s.
Adopt phosphorus to inject synthesis method and prepare the nearly stoicheiometry InP of 3.0kg polycrystalline material, preparation process condition is identical with embodiment 1, difference is to adopt single tube phosphorus bubble, generated time is 90 minutes, time is obviously long than using two-tube phosphorus bubble, its crystal ingot proportioning partly is less than the indium phosphide crystal ingot of two-tube phosphorus bubble synthetically grown, and synthetic effect also more two-tube phosphorus bubble is synthetic poor.Through the Hall test, its average carrier concentration is 3.07 * 10
15Cm
-3, average mobility is 4.23 * 10
3Cm
2/ V.s.
In addition, synthetic for single tube phosphorus bubble, the about 20g of residual phosphorus amount of two phosphorus bubble, two-tube phosphorus bubble is synthetic, and the residual phosphorus amount in the two phosphorus bubble is less than 3g.Through experiment statistics, the fried bubble rate of single tube phosphorus bubble reaches 20%, and the fried bubble rate of two-tube phosphorus bubble can be controlled in 3%, and is more safe and reliable.
The rich phosphorus InP of the synthetic 3.0kg of the fast synthesis method of indium phosphide polycrystalline material polycrystalline material, concrete operation step is:
The first step, in order to remove the factors such as packing to raw-material contamination, with MOS level dilute hydrochloric acid indium is carried out the light corrosion in surface first, then repeatedly boil cleaning with deionized water, to remove oxide compound and the residual impurity on indium surface, guarantee to test used high purity indium and reach the 6N purity, and the surface is without impurity such as dust.Indium after the cleaning is placed on and cures about 30min in the vacuum drying oven, and is for subsequent use.
Second step steeps the two-tube quartzy phosphorus that 6N phosphorus is housed in the phosphor source oven of packing into, and synthetic with two phosphorus bubbles, phosphor source oven adopts the molybdenum filament coiling, is quartzy round aecidioid;
The 3rd step, with high pressure single crystal growing furnace scrub, the heat-insulation system that then will design in advance, well heater, the crucible that indium is housed, synthetic used phosphor source oven and seed crystal and fluid-tight agent B
2O
3Put in the high pressure single crystal growing furnace burner hearth; The batch of starting material indium and phosphorus is respectively 2700g and 830g, dehydration boron oxide 400g;
Crucible is that diameter is round bottom or the flat crucible of 135mm;
The 4th step, close fire door, vacuumize with mechanical pump, after vacuum tightness reaches 60Pa, stop to vacuumize, fill the high-purity argon gas of 2MPa;
The 5th step, indium melt in the crucible is heated to 1375K, and behind temperature-stable, the phosphorus bubble is inserted in the indium melt, by observing bubble and the liquid level situation that bloats in the phosphorus bubble, the power of phosphor source oven heating is slowly increased, and the phosphorus heating vaporization in phosphorus is steeped is injected into reaction generation indium phosphide in the indium melt; Power heating curve in time always synthesizes 57 minutes time as shown in Figure 3;
The phosphorus bubble is inserted in the indium melt, and by progressively improving phosphor source oven power, power is controlled as shown in Figure 3, controls suitable phosphorus vapour pressure, makes phosphorus steam not too sharply enter melt, reduces the loss of phosphorus, and also bubbling is excessively unslow, prevents that the melt suck-back from causing fried bubble.Until a bubble synthetic complete after, mention and remove the phosphorus bubble.Melt temperature is suitably reduced, and then as above synthetic second phosphorus of method steeps.
The 6th step, after two phosphorus bubbles have synthesized, remove phosphor source oven, the decline seed crystal directly carries out the growth of liquid encapsulate Czochralski technique (LEC) crystal.
Two-tube quartzy phosphorus bubble comprises that the quartzy phosphorus container 1 for splendid attire solid phosphorus, two quartzy phosphorus steep pipe 2 and quartz cover 3; Phosphorus bubble pipe 2 bottoms are pierced in the described phosphorus container from the bottom of quartzy phosphorus container 1, and phosphorus bubble pipe 2 bottoms have the hole that phosphorus supply steam passes through, and the opening end of phosphorus bubble pipe 2 is positioned at outside the quartzy phosphorus container 1; Be tightly connected between phosphorus bubble pipe 2, quartz cover 3 and the quartzy phosphorus container 1.
The concrete technology condition is in the present embodiment: synthetic melt temperature: 1355～1395K, synthesis pressure: 3.5～4.5MPa, crucible rotation: 10～15rpm.
Take high-purity red phosphorus P (6N) and high purity indium In (6N) as starting material, with dehydration boron oxide (B
2O
3) be the fluid-tight agent, adopt the synthetic rich phosphorus InP polycrystalline of two-tube phosphorus method for implanting, its average carrier concentration is 3.51 * 10
15Cm
-3, average mobility is 4.15 * 10
3Cm
2/ V.s.
The fast synthesis method of indium phosphide polycrystalline material synthesizes the nearly stoicheiometry InP of 3.0kg polycrystalline material, and concrete operation step is:
The first step, in order to remove the factors such as packing to raw-material contamination, with MOS level dilute hydrochloric acid indium is carried out the light corrosion in surface first, then repeatedly boil cleaning with deionized water, to remove oxide compound and the residual impurity on indium surface, guarantee to test used high purity indium and reach the 6N purity, and the surface is without impurity such as dust, indium after the cleaning is placed on and cures about 30min in the vacuum drying oven, and is for subsequent use;
Second step steeps the two-tube quartzy phosphorus that 6N phosphorus is housed in the phosphor source oven of packing into, and synthetic with two phosphorus bubbles, phosphor source oven adopts the molybdenum filament coiling, is quartzy round aecidioid;
The 3rd step, with high pressure single crystal growing furnace scrub, the heat-insulation system that then will design in advance, well heater, the crucible that indium is housed, synthetic used phosphor source oven and seed crystal and fluid-tight agent B
2O
3Put in the high pressure single crystal growing furnace burner hearth; The batch of starting material indium and phosphorus is respectively 2700g and 780g, dehydration boron oxide 400g;
Crucible is that diameter is round bottom or the flat crucible of 135mm;
The 4th step, close fire door, vacuumize with mechanical pump, after vacuum tightness reaches 60Pa, stop to vacuumize, fill the high-purity argon gas of 2MPa;
The 5th step, indium melt in the crucible is heated to 1355K, and behind temperature-stable, the phosphorus bubble is inserted in the indium melt, by observing bubble and the liquid level situation that bloats in the phosphorus bubble, the power of phosphor source oven heating is slowly increased, and the phosphorus heating vaporization in phosphorus is steeped is injected into reaction generation indium phosphide in the indium melt; Power heating curve in time as shown in Figure 3, always the synthetic time is 53 minutes;
The phosphorus bubble is inserted in the indium melt, and by progressively improving phosphor source oven power, power is controlled as shown in Figure 3, controls suitable phosphorus vapour pressure, makes phosphorus steam not too sharply enter melt, reduces the loss of phosphorus, and also bubbling is excessively unslow, prevents that the melt suck-back from causing fried bubble.Until a bubble synthetic complete after, mention and remove the phosphorus bubble.Melt temperature is suitably reduced, and then as above synthetic second phosphorus of method steeps.
The 6th step, after two phosphorus bubbles have synthesized, remove phosphor source oven, the decline seed crystal directly carries out the growth of liquid encapsulate Czochralski technique (LEC) crystal.
Two-tube quartzy phosphorus bubble comprises that the quartzy phosphorus container 1 for splendid attire solid phosphorus, two quartzy phosphorus steep pipe 2 and quartz cover 3; Phosphorus bubble pipe 2 bottoms are pierced in the described phosphorus container from the bottom of quartzy phosphorus container 1, and phosphorus bubble pipe 2 bottoms have the hole that phosphorus supply steam passes through, and the opening end of phosphorus bubble pipe 2 is positioned at outside the quartzy phosphorus container 1; Be tightly connected between phosphorus bubble pipe 2, quartz cover 3 and the quartzy phosphorus container 1.
The concrete technology condition is in the present embodiment: synthetic melt temperature: 1355～1395K, synthesis pressure: 3.5～4.5Mpa, crucible rotation: 10～15rpm.
Take high-purity red phosphorus P (6N) and high purity indium In (6N) as starting material, with dehydration boron oxide (B
2O
3) be the fluid-tight agent, adopt the purity of the synthetic nearly stoicheiometry InP polycrystalline of two-tube phosphorus method for implanting higher, its average carrier concentration is 2.75 * 10
15Cm
-3, average mobility is 4.38 * 10
3Cm
2/ V.s.
Embodiment 4
The rich phosphorus InP of the synthetic 3.0kg of the fast synthesis method of indium phosphide polycrystalline material polycrystalline material, concrete operation step is:
The first step, in order to remove the factors such as packing to raw-material contamination, with MOS level dilute hydrochloric acid indium is carried out the light corrosion in surface first, then repeatedly boil cleaning with deionized water, to remove oxide compound and the residual impurity on indium surface, guarantee to test used high purity indium and reach the 6N purity, and the surface is without impurity such as dust.Indium after the cleaning is placed on and cures about 30min in the vacuum drying oven, and is for subsequent use.
Second step steeps the two-tube quartzy phosphorus that 6N phosphorus is housed in the phosphor source oven of packing into, and synthetic with two phosphorus bubbles, phosphor source oven adopts the molybdenum filament coiling, is quartzy round aecidioid;
The 3rd step, with high pressure single crystal growing furnace scrub, the heat-insulation system that then will design in advance, well heater, the crucible that indium is housed, synthetic used phosphor source oven and seed crystal and fluid-tight agent B
2O
3Put in the high pressure single crystal growing furnace burner hearth; The batch of starting material indium and phosphorus is respectively 2700g and 830g, dehydration boron oxide 400g;
Crucible is that diameter is round bottom or the flat crucible of 135mm;
The 4th step, close fire door, vacuumize with mechanical pump, after vacuum tightness reaches 60Pa, stop to vacuumize, fill the high-purity argon gas of 2MPa;
The 5th step, indium melt in the crucible is heated to 1395K, and behind temperature-stable, the phosphorus bubble is inserted in the indium melt, by observing bubble and the liquid level situation that bloats in the phosphorus bubble, the power of phosphor source oven heating is slowly increased, and the phosphorus heating vaporization in phosphorus is steeped is injected into reaction generation indium phosphide in the indium melt; Power heating curve in time always synthesizes 57 minutes time as shown in Figure 3;
The phosphorus bubble is inserted in the indium melt, and by progressively improving phosphor source oven power, power is controlled as shown in Figure 3, controls suitable phosphorus vapour pressure, makes phosphorus steam not too sharply enter melt, reduces the loss of phosphorus, and also bubbling is excessively unslow, prevents that the melt suck-back from causing fried bubble.Until a bubble synthetic complete after, mention and remove the phosphorus bubble.Melt temperature is suitably reduced, and then as above synthetic second phosphorus of method steeps.
The 6th step, after two phosphorus bubbles have synthesized, remove phosphor source oven, the decline seed crystal directly carries out the growth of liquid encapsulate Czochralski technique (LEC) crystal.
Two-tube quartzy phosphorus bubble comprises be used to the quartzy phosphorus container 1 of taking advantage of dress solid phosphorus, two quartzy phosphorus and steeps pipe 2 and quartz cover 3; Phosphorus bubble pipe 2 bottoms are pierced in the described phosphorus container from the bottom of quartzy phosphorus container 1, and phosphorus bubble pipe 2 bottoms have the hole that phosphorus supply steam passes through, and the opening end of phosphorus bubble pipe 2 is positioned at outside the quartzy phosphorus container 1; Be tightly connected between phosphorus bubble pipe 2 and the quartzy phosphorus container 1.
The concrete technology condition is in the present embodiment: synthetic melt temperature: 1355～1395K, synthesis pressure: 3.5～4.5MPa, crucible rotation: 10～15rpm.
Take high-purity red phosphorus P (6N) and high purity indium In (6N) as starting material, with dehydration boron oxide (B
2O
3) be the fluid-tight agent, adopt the synthetic rich phosphorus InP polycrystalline of two-tube phosphorus method for implanting, its average carrier concentration is 3.52 * 10
15Cm
-3, average mobility is 4.14 * 10
3Cm
2/ V.s.
Embodiment 5
The fast synthesis method of indium phosphide polycrystalline material synthesizes the nearly stoicheiometry InP of 3.0kg polycrystalline material, and concrete operation step is:
The first step, in order to remove the factors such as packing to raw-material contamination, with MOS level dilute hydrochloric acid indium is carried out the light corrosion in surface first, then repeatedly boil cleaning with deionized water, to remove oxide compound and the residual impurity on indium surface, guarantee to test used high purity indium and reach the 6N purity, and the surface is without impurity such as dust, indium after the cleaning is placed on and cures about 30min in the vacuum drying oven, and is for subsequent use;
Second step steeps the quartzy phosphorus of three pipes that 6N phosphorus is housed in the phosphor source oven of packing into, and synthetic with two phosphorus bubbles, phosphor source oven adopts the molybdenum filament coiling, is quartzy round aecidioid;
The 3rd step, with high pressure single crystal growing furnace scrub, the heat-insulation system that then will design in advance, well heater, the crucible that indium is housed, synthetic used phosphor source oven and seed crystal and fluid-tight agent B
2O
3Put in the high pressure single crystal growing furnace burner hearth; The batch of starting material indium and phosphorus is respectively 2700g and 780g, dehydration boron oxide 400g;
Crucible is that diameter is round bottom or the flat crucible of 135mm;
The 4th step, close fire door, vacuumize with mechanical pump, after vacuum tightness reaches 60Pa, stop to vacuumize, fill the high-purity argon gas of 2MPa;
The 5th step was heated to 1375K with indium melt in the crucible, and behind temperature-stable phosphorus was steeped pipe and insert in the indium melt, and by observing bubble and the liquid level situation that bloats in the phosphorus bubble, the phosphorus heating vaporization in phosphorus is steeped is injected into reaction generation indium phosphide in the indium melt; Total synthetic time is 47 minutes;
The phosphorus bubble is inserted in the indium melt, by progressively improving phosphor source oven power, control suitable phosphorus vapour pressure, make phosphorus steam not too sharply enter melt, reduce the loss of phosphorus, also bubbling is excessively unslow, prevents that the melt suck-back from causing fried bubble.Until a bubble synthetic complete after, mention and remove the phosphorus bubble.Melt temperature is suitably reduced, and then as above synthetic second phosphorus of method steeps.
The 6th step, after two phosphorus bubbles have synthesized, remove phosphor source oven, the decline seed crystal directly carries out the growth of liquid encapsulate Czochralski technique (LEC) crystal.
The concrete technology condition is in the present embodiment: synthetic melt temperature: 1355～1395K, synthesis pressure: 3.5～4.5Mpa, crucible rotation: 10～15rpm.
Take high-purity red phosphorus P (6N) and high purity indium In (6N) as starting material, with dehydration boron oxide (B
2O
3) be the fluid-tight agent, adopt the purity of the synthetic nearly stoicheiometry InP polycrystalline of two-tube phosphorus method for implanting higher, its average carrier concentration is 2.52 * 10
15Cm
-3, average mobility is 4.50 * 10
3Cm
2/ V.s.
Embodiment 6
The fast synthesis method of indium phosphide polycrystalline material synthesizes the nearly stoicheiometry InP of 3.0kg polycrystalline material, and concrete operation step is:
The first step, in order to remove the factors such as packing to raw-material contamination, with MOS level dilute hydrochloric acid indium is carried out the light corrosion in surface first, then repeatedly boil cleaning with deionized water, to remove oxide compound and the residual impurity on indium surface, guarantee to test used high purity indium and reach the 6N purity, and the surface is without impurity such as dust, indium after the cleaning is placed on and cures about 30min in the vacuum drying oven, and is for subsequent use;
Second step steeps the quartzy phosphorus of five pipes that 6N phosphorus is housed in the phosphor source oven of packing into, and synthetic with two phosphorus bubbles, phosphor source oven adopts the molybdenum filament coiling, is quartzy round aecidioid;
The 3rd step, with high pressure single crystal growing furnace scrub, the heat-insulation system that then will design in advance, well heater, the crucible that indium is housed, synthetic used phosphor source oven and seed crystal and fluid-tight agent B
2O
3Put in the high pressure single crystal growing furnace burner hearth; The batch of starting material indium and phosphorus is respectively 2700g and 780g, dehydration boron oxide 400g;
Crucible is that diameter is round bottom or the flat crucible of 135mm;
The 4th step, close fire door, vacuumize with mechanical pump, after vacuum tightness reaches 60Pa, stop to vacuumize, fill the high-purity argon gas of 2MPa;
The 5th step was heated to 1375K with indium melt in the crucible, and behind temperature-stable phosphorus was steeped pipe and insert in the indium melt, and by observing bubble and the liquid level situation that bloats in the phosphorus bubble, the phosphorus heating vaporization in phosphorus is steeped is injected into reaction generation indium phosphide in the indium melt; Total synthetic time is 43 minutes;
The phosphorus bubble is inserted in the indium melt, by progressively improving phosphor source oven power, control suitable phosphorus vapour pressure, make phosphorus steam not too sharply enter melt, reduce the loss of phosphorus, also bubbling is excessively unslow, prevents that the melt suck-back from causing fried bubble.Until a bubble synthetic complete after, mention and remove the phosphorus bubble.Melt temperature is suitably reduced, and then as above synthetic second phosphorus of method steeps.
The 6th step, after two phosphorus bubbles have synthesized, remove phosphor source oven, the decline seed crystal directly carries out the growth of liquid encapsulate Czochralski technique (LEC) crystal.
The concrete technology condition is in the present embodiment: synthetic melt temperature: 1355～1395K, synthesis pressure: 3.5～4.5Mpa, crucible rotation: 10～15rpm.
Take high-purity red phosphorus P (6N) and high purity indium In (6N) as starting material, with dehydration boron oxide (B
2O
3) be the fluid-tight agent, adopt the purity of the synthetic nearly stoicheiometry InP polycrystalline of two-tube phosphorus method for implanting higher, its average carrier concentration is 2.50 * 10
15Cm
-3, average mobility is 4.52 * 10
3Cm
2/ V.s.
Claims (10)
1. the fast synthesis method of an indium phosphide polycrystalline material is characterized in that may further comprise the steps:
The first step is carried out surface cleaning processing to indium, with the indium dry for standby after cleaning;
Second step steeps the quartzy phosphorus of the multitube that phosphorus is housed in the phosphor source oven of packing into, and the quartzy phosphorus bubble of multitube comprises at least two quartzy phosphorus bubble pipes;
The 3rd step, with high pressure single crystal growing furnace scrub, the heat-insulation system that then will design in advance, well heater, the crucible that indium is housed, synthetic used phosphor source oven and seed crystal and fluid-tight agent B
2O
3Put in the high pressure single crystal growing furnace burner hearth;
In the 4th step, to vacuumizing in the stove, then fill high-purity argon gas;
In the 5th step, phosphorus is steeped interior phosphorus heating vaporization be injected into reaction generation indium phosphide in the indium melt;
In the 6th step, carry out the crystal growth.
2. the fast synthesis method of indium phosphide polycrystalline material as claimed in claim 1 is characterized in that: the first step, indium is carried out surface treatment to remove oxide compound and the residual impurity on indium surface, and guarantee that indium reaches the 6N purity, and the surface is without dust impurity.
3. the fast synthesis method of indium phosphide polycrystalline material as claimed in claim 1, it is characterized in that: second step, the purity of phosphorus are 6N.
4. the fast synthesis method of indium phosphide polycrystalline material as claimed in claim 1 is characterized in that: the vacuum tightness in the 4th step in the stove is less than 10
2Pa.
5. the fast synthesis method of indium phosphide polycrystalline material as claimed in claim 1 is characterized in that: the high-purity argon gas that fills 2MPa in the 4th step in the stove.
6. the fast synthesis method of indium phosphide polycrystalline material as claimed in claim 1, it is characterized in that: the 5th step was heated to preset temperature with indium melt in the crucible, behind temperature-stable quartzy phosphorus bubble pipe is inserted in the indium melt, the phosphorus heating vaporization in phosphorus is steeped is injected into reaction generation indium phosphide in the indium melt.
7. the fast synthesis method of indium phosphide polycrystalline material as claimed in claim 6 is characterized in that: preset temperature is 1355～1395K described in the 5th step.
8. the fast synthesis method of indium phosphide polycrystalline material as claimed in claim 1 is characterized in that: adopt high-pressure liquid encapsulation pulling method to carry out the crystal growth in the 6th step.
9. such as the quartzy phosphorus bubble of the used multitube of the fast synthesis method of each indium phosphide polycrystalline material in the claim 1～8, comprise quartzy phosphorus container (1) and quartz cover (3) for splendid attire solid phosphorus; It is characterized in that: also comprise at least two quartzy phosphorus bubble pipes (2), described phosphorus bubble pipe (2) bottom is pierced in the described phosphorus container from the bottom of quartzy phosphorus container (1), phosphorus bubble pipe (2) bottom has the hole that phosphorus supply steam passes through, and the opening end of described phosphorus bubble pipe (2) is positioned at outside the quartzy phosphorus container (1); Be tightly connected between described phosphorus bubble pipe (2), quartz cover (3) and the quartzy phosphorus container (1).
10. the quartzy phosphorus bubble of multitube as claimed in claim 9 is characterized in that: comprise two quartzy phosphorus bubble pipes (2).
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| CN108358180A (en) * | 2017-12-08 | 2018-08-03 | 中国电子科技集团公司第十三研究所 | Phosphide injection synthetic method in situ is carried out using carrying gas |
| CN108360073A (en) * | 2017-12-08 | 2018-08-03 | 中国电子科技集团公司第十三研究所 | A kind of preparation method of compound semiconductor polycrystal material |
| CN110760932A (en) * | 2019-11-22 | 2020-02-07 | 中国电子科技集团公司第十三研究所 | Method for preparing indium phosphide crystal by indium phosphide mixture |
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| CN117702274A (en) * | 2024-02-05 | 2024-03-15 | 浙江康鹏半导体有限公司 | Growth process of indium phosphide crystal |
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| CN103160924A (en) * | 2013-03-15 | 2013-06-19 | 杭州电子科技大学 | Multi-tube device for quickly synthesizing indium phosphide polycrystal phosphorus bubbles |
| CN104404623A (en) * | 2014-11-26 | 2015-03-11 | 中国电子科技集团公司第十三研究所 | Phosphorus bubble lifting device for indium phosphide single-crystal furnace |
| US10648100B1 (en) * | 2017-12-08 | 2020-05-12 | The 13Th Research Institute Of China Electronics Technology Group Corporation | Method for carrying out phosphide in-situ injection synthesis by carrier gas |
| CN108358180A (en) * | 2017-12-08 | 2018-08-03 | 中国电子科技集团公司第十三研究所 | Phosphide injection synthetic method in situ is carried out using carrying gas |
| CN108360073A (en) * | 2017-12-08 | 2018-08-03 | 中国电子科技集团公司第十三研究所 | A kind of preparation method of compound semiconductor polycrystal material |
| WO2019109366A1 (en) * | 2017-12-08 | 2019-06-13 | 中国电子科技集团公司第十三研究所 | Method for in-situ injection and synthesis of phosphide by using bearing gas |
| CN108358180B (en) * | 2017-12-08 | 2019-08-02 | 中国电子科技集团公司第十三研究所 | Phosphide injection synthetic method in situ is carried out using carrying gas |
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| WO2021098348A1 (en) * | 2019-11-22 | 2021-05-27 | 中国电子科技集团公司第十三研究所 | Method for preparing indium phosphide crystal using indium-phosphorus mixture |
| US11781240B2 (en) | 2019-11-22 | 2023-10-10 | The 13Th Research Institute Of China Electronics Technology Group Corporation | Method for preparing indium phosphide crystal by utilizing indium-phosphorus mixture |
| CN111424310A (en) * | 2020-06-02 | 2020-07-17 | 中国电子科技集团公司第十三研究所 | Method for synthesizing indium phosphide by liquid phosphorus injection method |
| WO2021243873A1 (en) * | 2020-06-02 | 2021-12-09 | 中国电子科技集团公司第十三研究所 | Method for synthesizing indium phosphide by liquid phosphorus injection method |
| CN111424310B (en) * | 2020-06-02 | 2022-02-15 | 中国电子科技集团公司第十三研究所 | Method for synthesizing indium phosphide by liquid phosphorus injection method |
| CN112680790A (en) * | 2020-12-07 | 2021-04-20 | 宁波建锡新材料有限公司 | Synthesis method of indium phosphide semiconductor material |
| CN112708935A (en) * | 2020-12-23 | 2021-04-27 | 中国电子科技集团公司第十三研究所 | Control method of semiconductor phosphide injection synthesis system |
| CN117702274A (en) * | 2024-02-05 | 2024-03-15 | 浙江康鹏半导体有限公司 | Growth process of indium phosphide crystal |
| CN117702274B (en) * | 2024-02-05 | 2024-04-30 | 浙江康鹏半导体有限公司 | Growth process of indium phosphide crystal |
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