CN100344802C - Process for preparing lead sulfur family compound semiconductor single crystal - Google Patents
Process for preparing lead sulfur family compound semiconductor single crystal Download PDFInfo
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- CN100344802C CN100344802C CNB2005100282314A CN200510028231A CN100344802C CN 100344802 C CN100344802 C CN 100344802C CN B2005100282314 A CNB2005100282314 A CN B2005100282314A CN 200510028231 A CN200510028231 A CN 200510028231A CN 100344802 C CN100344802 C CN 100344802C
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Abstract
The present invention relates to a growth and preparation method of lead chalcogenide semi-conducting crystals, which belongs to the technical field of semiconductor single crystal preparation progress. In the present invention, high-purity metallic lead powder and the powder of chalcogen S or Se or Te taken and weighed according to a certain mole ratio is put in a quartz tube which is vacuumized, the vacuum degree in the quartz tube reaches 0.001 Pa or 0.0001 Pa, the quartz tube is put in a vertical heating furnace, and the high-purity metallic lead powder and the powder of chalcogen S or Se or Te is melted and reacts to generate lead chalcogenide of PbS or PbSe or PbTe; the lead chalcogenide of PbS or PbSe or PbTe is heated to the temperature of 20 DEG C above the fusing point and is kept in a molten state, and the temperature is lowered to the temperature of the fusing point again; a motor is started, the quartz tube is lifted and pulled at the speed of 5MM /day to 7MM /day, and a semiconductor single crystal of which the diameter is 25MM to 30MM is taken out after 7 days to 10 days. In the method of the present invention, the semiconductor single crystal essentially grows and is prepared by melt evaporating and vapor deposition, and the semiconductor single crystal grows according to certain crystal surfaces or certain crystal directions to form semiconductor single crystal material. Large-size single crystals prepared in the method of the present invention can be used for high-integration detectors or sensitive functional devices.
Description
Technical field
The present invention relates to a kind of growth and preparation method of sulfur family compound semiconductor single crystal of lead, plumbous chalcogenide PbS, PbSe or PbTe belong to semiconductor monocrystal fabricating technology field.
Background technology:
Plumbous chalcogenide, comprise PbS, PbSe and PbTe compound semiconductor, its energy gap is narrower, can be used for making various infrared eyes, laser apparatus, field effect transistor, temperature-sensitive device and other various integrated devices of function with light, magnetic, electricity, sound overall characteristic.This type of material rises abroad as far back as the seventies in 20th century and has report in the document.The growth method of semiconductor monocrystal includes vapor transportation growth, sublimation-grown, Bridgman (Bridgeman) method, liquid phase and vapour phase epitaxy, molecular beam epitaxy and other Several Methods just so far.With regard to vapour growth, people such as Ya Xina (L.V.Yashina et.al.) work literary composition " application of bulk semiconductor VLS growing technology " Journal of Crytal Growth, vol.252, discuss to some extent among the p68 (2003), but it is only similar in its VLS method with growing by zone melting, all there is crystal growth in its melt at two ends, and the crystal of growth is not to be monocrystalline.
Yet, as a kind of extremely useful, both can be used as a kind of base material, the sulfur family compound semiconductor single crystal preparation methods of the lead of the large-size of constructible set one-tenthization again, rare so far report.Generally speaking, the size that monocrystal material gets with various vapor phase process growing and preparing is often less, and growth cycle is long.It is investigated, up to now, as if impossible as if the sulfur family compound semiconductor single crystal of the lead that will reach the above diameter of φ 20mm.Therefore, because the restriction of monocrystalline size will make this type of small size semiconductor single crystal material be built into the detector or the sensitive function device of various high integration, just there has been certain difficulty.
Past, what vapor phase growth method was commonly used is subliming method, it mainly is to carry out under the temperature difference situation that keeps certain, rolls up the argumentation of being done in 283 pages of (2000) papers " physical vapor of Pb-Te-Se transports experimental study and thermochemistry model " as people such as Pa Luoke (W.Palog et al) at " crystal growth magazine " 216.Process of growth is the source with the chalcogenide xln (polycrystal) of lead, put into seed crystal then and grow greatly as the parent crystal of single crystal growing, but the crystal that this method obtains often is no more than 10mm.Also having a kind of is the growth that utilizes the vapour transport method, as driving for transporting carrier with AgI steam, similar to above-mentioned subliming method, the steam of the chalcogenide of lead is transported on the crystal grain, and then growth step by step, but the speed of its growth is still slower, and the crystalline size of growth is also less, and the cycle is also long.Ask Bei Dengren (D.Stober et al) in the content described in the paper " by PbTe under the influence of AgI vapour phase and the reaction of the CHEMICAL TRANSPORT during the PbSe crystal growth " of " crystal growth magazine " 121 volumes 565 pages (1992) like that.
Summary of the invention
The above-mentioned situation of backbone, the growth and the preparation method that the purpose of this invention is to provide a kind of sulfur family compound semiconductor single crystal of lead also promptly solve and it are grown into have certain crystalline phase orientation, larger-size, monocrystalline growing process that growth velocity is relatively large again.
The preparation method of the sulfur family compound semiconductor single crystal of a kind of lead of the present invention that is to say the method with method of evaporation vapor deposition growth monocrystalline, it is characterized in that having following technological process and step:
A. at first with highly purified metallic lead and highly purified sulfur family element, comprise S, Se or Te, take by weighing weight, both are positioned over the lower end of silica tube by certain mol proportion; Place the sulfur family compound semiconductor seed body of a lead in addition at the narrow tubule eck of the contraction place on interior silica tube top, its crystal face may be selected to be (100), (110) or (111) any;
B. at the base of the interior silica tube of bottom-open and the tube wall place of outer silica tube bottom suitable position, weld, with fixing interior silica tube with brazing mode; Silica tube top is shunk narrow thin neck mouth and is vacuumized with vacuum pump outside then, makes the vacuum tightness in the silica tube reach 10
-4Pa or 10
-5Pa carries out tube sealing subsequently;
C. above-mentioned silica tube is totally placed in the vertical heater, the top cold zone and the high-temperature zone, bottom of vertical heater are controlled by the fusing point that specifically is heated compound, and generally its mean temperature difference is controlled between 5～50 ℃ or greater than 50 ℃:
D. after silica tube totally being put into vertical heater, heat up with 10 ℃/component velocity earlier, arrive above 20 ℃ of melting point compound, keep fusing, need the time approximately, and then be cooled to fusing point:
E. the back hotwire lifts silica tube, promotes with 5～7mm/ days speed, reach 7～10 days after, taking out diameter is the sulfur family compound semiconductor single crystal of the lead of 25～30mm.
In the inventive method, use raw material Pb and the sulfur family element (S, Se or Te) of high purity 6N (i.e. 69 purity), in silica tube, be heated the molten concurrent biochemical reaction of touching during beginning, generate the compound of PbX, X is represented as any chemical element of S, Se or Te, the PbX compound of Sheng Chenging is under heating condition then, arrive above 20 ℃ of its fusing point, it is fully melted and evaporate, steam rises and arrives on the PbX seed crystal of silica tube upper ends, carry out vapor deposition, grow into the PbX semiconductor monocrystal, prepared PbX semiconductor monocrystal has bigger size.Research trial is the result show, the monocrystalline that the inventive method makes than the monocrystalline size of the Bu Shi method of knowing at present, subliming method, gas-phase transport method more greatly, and growth velocity is also very fast.Be difficult in the PbX compound semiconductor single crystal that the inventive method makes find have polycrystalline to be sandwiched in wherein.
The growth of the sulfur family compound semiconductor single crystal of a kind of lead of the present invention and preparation method finish in the isolated plant of a particular design.
Embodiment
Now with the growth and the preparation method of chalcogenide PbX (X represents S, Se or the Te) semiconductor monocrystal of lead of the present invention, after being described in by embodiment.
Embodiment 1
Preparation PbS semiconductor monocrystal:
(1) adopts high purity 99.9999% (6N, i.e. 69 purity) metal Pb powder and chemical element S powder than weighing, are wherein considered the volatilization of S by 1: 1 mole (mol), the S powder increases by 0.1% amount usually again, and the raw material that both is positioned over the lower end of outer silica tube melts in the reaction zone; Place PbS semi-conductor seed body in addition at the narrow tubule eck of the contraction place on interior silica tube top, its crystal face may be selected to be (100), (110) or (111) any;
(2) at the base of the interior silica tube of bottom-open and the tube wall place of outer silica tube bottom suitable position, weld, with fixing interior silica tube with brazing mode; Silica tube top is shunk narrow thin neck mouth place and is vacuumized with vacuum pump outside then, makes the vacuum tightness in the silica tube reach 10
-4Pa or 10
-5Pa carries out tube sealing subsequently.
(3) above-mentioned silica tube totally is positioned in the vertical heater, the top cold zone of vertical heater and high-temperature zone, bottom, its mean temperature difference is controlled between 5～50 ℃ or is slightly larger than 50 ℃;
(4) silica tube is totally put into vertical heater after, heat up earlier with 10 ℃/component velocity, rise 20 ℃ again after arriving the fusing point of 1114 ℃ of PbS, rise to 1134 ℃, keep fusing, need 1 day time approximately, and then be cooled to 1114 ℃ of melting temperatures;
(5) hotwire then, by the pulley gear that outer silica tube upper end connects, it is overall to lift silica tube, promotes with 5～7mm/ days speed, reach 7～10 days after, can form the place, district in the single crystal growing on interior silica tube top and obtain well-grown PbS semiconductor monocrystal.Be of a size of φ 25～30mm according to detecting single crystal diameter.
Embodiment 2
It is identical that present embodiment prepares step and the foregoing description 1 of PbSe semiconductor monocrystal.Different is: adopt the metal Pb powder and the chemical element Se powder of 6N purity, by 1: 1mol is than weighing, and wherein the Se powder increases by 0.1% after amount; Raw material Pb and Se are heated to 1065 ℃ of PbSe fusing points in vertical heater, rise 20 ℃ again after reaching fusing point, rise to 1085 ℃, keep fusing, reduce to 1065 ℃ of melting temperatures after 1 day time again.
Prepared PbSe semiconductor monocrystal is according to detecting its single crystal diameter size average out to 25～30mm.
Embodiment 3
Preparation PbTe semiconductor monocrystal:
It is identical that present embodiment prepares step and the foregoing description 1 of PbTe semiconductor monocrystal.Different is: adopt the powdered metallic lead and the chemical element Te powder of 6N purity, by 1: 1mol is than weighing, and wherein the Te powder increases by 0.1% after amount; Raw material Pb and Te pine for being heated to 924 ℃ of PbTe fusing points in vertical adding, and rise 20 ℃ again after reaching fusing point, are warming up to 944 ℃, keep fusing, are cooled to 924 ℃ of melting temperatures after 1 day time again.
Prepared PbTe semiconductor monocrystal is according to detecting its single crystal diameter size average out to 25～30mm.
The inventive method essence is the growth for preparing semiconductor monocrystalline by melt evaporation vapor deposition, and the monocrystal material that forms by the growth of certain crystal face crystal orientation.The semiconductor single crystal material of the prepared large-size of the inventive method helps the development and application in various high integration detectors or sensitive function devices field.
Claims (1)
1. the preparation method of the sulfur family compound semiconductor single crystal of a lead is characterized in that having following technological process and step:
A. at first with 99.9999% highly purified metallic lead and highly purified sulfur family element, comprise S, Se or Te, take by weighing weight, both are positioned over the lower end of silica tube by certain mol proportion; Place the sulfur family compound semiconductor seed body of a lead in addition at the narrow tubule eck of the contraction place on interior silica tube top, its crystal face may be selected to be (100), (110) or (111) any;
B. at the base of the interior silica tube of bottom-open and the tube wall place of outer silica tube bottom suitable position, weld, with fixing interior silica tube with brazing mode; Silica tube top is shunk narrow thin neck mouth and is vacuumized with vacuum pump outside then, makes the vacuum tightness in the silica tube reach 10
-4Pa or 10
-5Pa carries out tube sealing subsequently;
C. above-mentioned silica tube is totally placed in the vertical heater, the top cold zone and the high-temperature zone, bottom of vertical heater are controlled by the fusing point that specifically is heated compound, and generally its mean temperature difference is controlled between 5～50 ℃;
D. after silica tube totally being put into vertical heater, heat up with 10 ℃/component velocity earlier, arrive above 20 ℃ of melting point compound, keep fusing, need the time approximately, and then be cooled to fusing point;
E. the back hotwire lifts silica tube, promotes with 5～7mm/ days speed, reach 7～10 days after, taking out diameter is the sulfur family compound semiconductor single crystal of the lead of 25～30mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100282314A CN100344802C (en) | 2005-07-28 | 2005-07-28 | Process for preparing lead sulfur family compound semiconductor single crystal |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2005100282314A CN100344802C (en) | 2005-07-28 | 2005-07-28 | Process for preparing lead sulfur family compound semiconductor single crystal |
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|---|---|
| CN1737221A CN1737221A (en) | 2006-02-22 |
| CN100344802C true CN100344802C (en) | 2007-10-24 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100368601C (en) * | 2006-08-31 | 2008-02-13 | 山东大学 | Autoclave synthesis method of sulfur group compound |
| CN106082141A (en) * | 2016-06-06 | 2016-11-09 | 浙江大学 | A kind of preparation method of the atomic ratio compound semiconductors such as IV VI races |
| CN114059157B (en) * | 2020-07-31 | 2022-12-13 | 清华大学 | Method for preparing transition metal chalcogenide crystal |
| CN115991603A (en) * | 2022-11-24 | 2023-04-21 | 安徽大学绿色产业创新研究院 | Preparation method of Cr/Te co-doped PbSe-based thermoelectric material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01138199A (en) * | 1987-11-24 | 1989-05-31 | Nippon Telegr & Teleph Corp <Ntt> | Lead-tin-tellurium based semiconductor single crystal |
| JPH08283094A (en) * | 1995-04-13 | 1996-10-29 | Nippon Telegr & Teleph Corp <Ntt> | Production of single crystal and device therefor |
| CN1136092A (en) * | 1996-04-11 | 1996-11-20 | 中国科学院上海技术物理研究所 | Manufacture of lead telluride with high tellurium content |
| CN1173878C (en) * | 2002-03-27 | 2004-11-03 | 吉林大学 | High pressure synthesis of lump nano semiconductor PbTe material |
-
2005
- 2005-07-28 CN CNB2005100282314A patent/CN100344802C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01138199A (en) * | 1987-11-24 | 1989-05-31 | Nippon Telegr & Teleph Corp <Ntt> | Lead-tin-tellurium based semiconductor single crystal |
| JPH08283094A (en) * | 1995-04-13 | 1996-10-29 | Nippon Telegr & Teleph Corp <Ntt> | Production of single crystal and device therefor |
| CN1136092A (en) * | 1996-04-11 | 1996-11-20 | 中国科学院上海技术物理研究所 | Manufacture of lead telluride with high tellurium content |
| CN1173878C (en) * | 2002-03-27 | 2004-11-03 | 吉林大学 | High pressure synthesis of lump nano semiconductor PbTe material |
Non-Patent Citations (1)
| Title |
|---|
| 热电材料碲化铅PBTE的晶体生长及其物理性质研究 李锡华等，浙江大学学报 工学版，第33卷第5期 1999 * |
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| CN1737221A (en) | 2006-02-22 |
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Granted publication date: 20071024 Termination date: 20100728 |