CN1172174A - Method for solid regional melting growth of 1-3 micron Te-Cd-Hg crystal material - Google Patents
Method for solid regional melting growth of 1-3 micron Te-Cd-Hg crystal material Download PDFInfo
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- CN1172174A CN1172174A CN 97106362 CN97106362A CN1172174A CN 1172174 A CN1172174 A CN 1172174A CN 97106362 CN97106362 CN 97106362 CN 97106362 A CN97106362 A CN 97106362A CN 1172174 A CN1172174 A CN 1172174A
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Abstract
The present invention belongs to the field of compound semiconductor and crystal growth technology. It provides a preparation methd of 1-3 micrometer Te-Cd-Hg crystal material. Said invented technological process includes: cleaning material tube, baking, compounding, air-bleeding and sealing tube; synthesizing, changing tube, monocrystal growing, slicing and heat treatment. Said invention solves the key technical problems of up-down background temp. selection, molten zone width selection, design of special form of elliptical quartz material tube, and crystal bidirectional rotation, etc.. Said prepared material possesses excellent properties, so that it is suitable for crystal material for making Te-Cd-Hg short-wave infrared detector.
Description
The invention belongs to inorganic chemistry and field of crystal growth, relate to the growth of II-VI family tellurium compound semiconductor growing and zone melting single-crystal, is a kind of preparation method who is used for the Te-Cd-Hg crystal material of short-wave infrared detector.Te-Cd-Hg (Hg
1-XCd
XTe, MCT) material is an II-VI family tellurium compound low-gap semiconductor.It is at the 1-3 micron, the 3-5 micron, and three atmospheric windows of 8-14 micron have extremely important application.Especially in the aerospace remote sensing technology, military technique, optical-fibre communications, the realistic meaning that laser technology field has a wide range of applications.Document " THM; a breakthrough in HgCdTe bulk metallurgy " (J.Vac.Sci.Tech.A3 (1), Jan/Feb 1985), " MCT single crystal growth by Traveling HeaterMethod with a mercury reservoir " (Journal of Crystal Growth 99 (1990)), " A newapproach to crystal growth of HgCdTe by the traveling heater method " reports such as (Journal ofCrystal Growth 114 (1991)) shows that the Hg-Cd-Te material technology of growth X＜0.4 and X＞0.6 has been mature on the whole, and it is few to prepare the Te-Cd-Hg crystal material foreign literature report of x=0.4～0.6 with body material growth technique, not quite clear from its longitudinal uniformity of existing report not good (material of x=0.4～0.6 is less than 2cm) specific performance parameter.
The object of the present invention is to provide a kind of preparation response wave band is 1-3 micron (x=0.4～0.6) Te-Cd-Hg (Hg
1-XCd
XTe) method of crystalline material.
Solid zone melting method growth tellurium-cadmium-mercury crystal.Long brilliant stove makes a bit of polycrystalline fusing, and silica tube descends with constant rate of speed.In fact crystal growth is exactly that the polycrystalline ingot constantly melts, and the process that solid-liquid interface is moved on constantly.
In order to discuss conveniently, we simplify actual procedure:
1). solid-liquid interface is the plane;
2). the ingot walking speed is enough slow, so that molten matter uniform distribution in the melting zone, and crystal is grown in quasi-stationary process;
3). in the crystal growing process, Tc is constant;
4). equilibrium segregation coefficient K is a constant;
5) .L is an ingot length;
6) .a is the melting zone width;
7) .z is the crystalline along slope coordinate;
Then in 0＜Z＜L-a zone, system is the solute nonconservative system, and promptly along with the carrying out of long brilliant process, the solute in monocrystalline-melt system constantly increases.The component of monocrystalline distributes and satisfies equation:
X(Z)＝X
L[1-(1-K)exp(-KZ/a)](1)
X wherein
LBe the original ingredient component.
And in L-a＜Z＜L zone, long brilliant process can be considered the conservative system of solute, and promptly the solute in monocrystalline-melt system is constant.This moment, the component of monocrystalline distributed satisfied:
X(Z)b＝Kb(1-Z/L)
K-1 (2)
Wherein b is a constant, can be determined by final condition.
We can draw the long brilliant vertical component distribution of solid zone melting method by above-mentioned simple one-dimensional model.As seen the head of ingot is high component crystal, and the melting zone width is big more, the high constituent materials that obtains also many more (long L is certain for ingot).If the melting zone is dwindled, just can obtain and the uniform MCT crystal of the corresponding to component of original stoicheiometry.Therefore by regulating furnace, can control the long brilliant component of " solid area is molten " technology and distribute.
Certainly this is the simplest model.In the brilliant process of the molten actual (tube) length of solid area, segregation coefficient, Tc are all relevant with crystal composition.
Same stoicheiometry when original ingot solute is not a constant, but with the function of variable in distance, and then the materials chemistry proportioning of district after molten also will change, and this provides theoretical foundation for CdTe replenishes technology.
Description of drawings of the present invention is as follows:
Fig. 1 is a process flow diagram of the present invention;
Fig. 2 is the vertical distribution schematic diagram in the brilliant furnace temperature of length field of crystal growth of the present invention;
Fig. 3 is Hg
1-XCd
XTe crystalline component-temperature X-T phasor.
Below in conjunction with accompanying drawing the present invention is done and to specify.
The present invention reaches the purpose of crystal growth by following process technology scheme:
Technical process comprises: the material pipe cleans, baking, and batching, the exhaust tube sealing, synthetic, replace tubes, single crystal growing, section, thermal treatment.(accompanying drawing 1)
A). material pipe cleans: will expect that effective chloroazotic acid soaks and use washed with de-ionized water more than ten times after 24 hours;
B). the baking of material pipe: cleaned material pipe is standby after 10 hours in baking under 80 ℃ the condition in baking box;
C). batching: carry out Hg by the X=0.2 component
1-XCd
XEach element weighing of Te.Other adds additional mercury 20mg/cm3;
D). the exhaust tube sealing: material pipe adds and is enclosed in that exhaust is more than 4 hours on the vacuum system after the element that weighs up, and vacuum remains on the 1.0E-6Pa condition in the system, adds liquid nitrogen and seals after half an hour;
E). synthetic: synthesis temperature is 850 ℃ when synthetic, reach swing behind the synthesis temperature obtain more than 4 hours component evenly, the polycrystalline material of compact structure;
F). replace tubes: will synthesize the particle of 1 cubic millimeter of good material knock, feeding pipe replenishes 10 gram CdTe every 3cm;
G). single crystal growing: with polycrystal growing single-crystal (seeing accompanying drawing 2) in long brilliant stove, the melting zone temperature was 850 ℃ when length was brilliant, the melting zone width is about 2.5 centimetres, last ambient temperature is lower than about 60 ℃ in melting zone, following ambient temperature is then got its thermograde near 70 ℃/cm, and crystalline growth velocity is 6 millimeters/day, utilizes the effect of segregation to obtain the MCT material of big component, in the material growth, use oval flat tube, use the two-way rotating technique of crystal for making crystal thermally equivalent in process of growth;
H). section: will grow good crystal and cut into slices from interior taking-up of material pipe, slice thickness is generally about 1mm;
I). thermal treatment:, handled 2 months according to the slice, thin piece (400 ℃) under the rational heat treatment temperature that densimetry filters out;
The present invention has following major technique key: 1. the synthetic technology key of high component MCT starting materials according to the theory and practice of crystal growth as can be known, the grow Te-Cd-Hg crystal material of X=0.40～0.60, at first must solve the composition problem of material, from the T-X phasor (accompanying drawing 3) as can be seen, along with former component of expecting (X value) increases, its synthesis temperature, mercury vapor pressure is all raising in the material pipe, and its synthesis temperature of MCT material of synthetic X=0.40～0.60 is greater than 900 ℃.Utilize quartzy material pipe to synthesize and to realize.The synthetic former directly molten crystal growing technology in district of expecting of this process using small component (X=0.20) safety.Thereby solved the synthetic difficult problem of high component.2. the selection of solid area process of smelting technical background temperature
The selection of the best furnace of long brilliant stove has decisive meaning for " solid zone melting method " long brilliant technology.Last background has temperature value an of the best and melting zone temperature to be complementary.It is better that last ambient temperature is lower than about 60 ℃ in melting zone.Following ambient temperature then get its thermograde near 70 ℃/cm for well.Thereby obtain the optimum temperature profile of continuous growth.3. the selection of melting zone width:
Melting zone width (relevant with furnace) size is crucial to this technology high constituent materials of growing.The uniform material of the more little vertical component of easy more acquisition of this width, but can't obtain the above high constituent materials in X＞0.40.Can obtain goodish result when selecting this width to be about 2.5 centimetres.4. long spar English tubular construction
In the Hg-Cd-Te material growth technique.Through the computer simulation analysis that solid-liquid interfacial state in the crystal growing process is arranged in the circular silica tube under the solute condition is drawn, this type of material pipe is along with diameter reduces, and solid-liquid interface is the spill of getting deeply stuck in, the horizontal component of formation crystal inhomogeneous.This brings unfavorable factor to crystal growth.As use oval flat tube, through computer simulation, it is quite smooth that the interface becomes, and the horizontal component uniformity of the crystalline of growth improved have excellent results.5. the two-way rotating technique of crystal
Because the furnace temperature lateral distribution (mainly being the melting zone temperature) of long brilliant stove has fluctuating.Therefore with electronically controlled two-way Crystal Rotation device, make crystal thermally equivalent in process of growth.Its effect is the flatness that has improved the interface greatly, has improved horizontal component uniformity of crystalline and structural integrity.6.CdTe replenish growth
According to crystal growth theories and put into practice work as can be known, big component crystal is to rely on the effect of segregation because zone melting method is grown, and the big component amount of crystals that grows when the starting materials in the material pipe is one-component X=0.2 is limited.Long former of general 8cm expected and only can obtain the material of X＞0.4-0.6 of 2-4cm.In order to improve big component crystalline ratio, we adopt the CdTe replenishment.Promptly replenish CdTe between expecting in that each section is former.The crystal of the big component that obtains surpasses 7cm, has improved big component crystalline ratio.
1-3 micron Te-Cd-Hg crystal material material after thermal treatment of the inventive method growth reaches following technical indicator, is very suitable for the manufacturing of the infrared mercury-cadmium tellurid detector of response wave band 1-3 micron:
Diameter: φ 15～φ 20mm;
Component X:0.4～0.6;
Electric property: carrier concentration N (77K): 2.0E+13～1.5E+14cm-3;
Mobility [mu] (77K):＞1.0E+1cm
2/ v Sec;
Resistivity p (77K): 5.0E-1～1.0E+2 Ω cm;
Transmitance (thickness of sample 0.7-1.0mm):＞40% (300K);
The crystalline structure integrity is good;
Laterally component X homogeneity is better than 0.01;
The about 7cm of length of material of vertical X=0.40～0.60.
The present invention has following beneficial effect:
1. " solid area is molten " is the effective technical way of preparation 1-3 micron Te-Cd-Hg crystal material.Key issues such as the design of the selection of the selection of ambient temperature, melting zone width about the invention solves, the extraordinary shape of oval quartzy material pipe, the two-way rotation of crystal.The material property of preparation is good.
2. " solid area process of smelting " can also obtain to respond respectively the high-quality Te-Cd-Hg crystal material of 1-20 micron infrared band in an ingot outside the big component crystalline material of growth." solid area process of smelting " has very outstanding advantage on engineering is used.
3. the infrared eye of fine 1-3 micron Te-Cd-Hg crystal material manufacturing has very big using value in fields such as remote sensing technology, optical-fibre communications, laser technology, physical basis researchs.
Claims (2)
1. the method for solid regional melting growth of 1-3-3 micron Te-Cd-Hg crystal material, technical process comprises: the material pipe cleans, baking, batching, the exhaust tube sealing, synthetic, replace tubes, single crystal growing, section, thermal treatment is characterized in that:
A). material pipe cleans: will expect that effective chloroazotic acid soaks and use washed with de-ionized water more than ten times after 24 hours;
B). the baking of material pipe: cleaned material pipe is standby after 10 hours in baking under 80 ℃ the condition in baking box;
C). batching: carry out Hg by the X=0.2 component
1-XCd
XEach element weighing of Te, other adds additional mercury 20mg/cm3
D). the exhaust tube sealing: material pipe adds and is enclosed in that exhaust is more than 4 hours on the vacuum system after the element that weighs up, and vacuum remains on the 1.0E-3Pa condition in the system, adds liquid nitrogen and seals after half an hour;
E). synthetic: synthesis temperature is 850 ℃ when synthetic, reach swing behind the synthesis temperature obtain more than 4 hours component evenly, the polycrystalline material of compact structure;
F). replace tubes: will synthesize the particle of 1 cubic millimeter of good material knock, feeding pipe replenishes 10 gram CdTe every 3cm;
G). single crystal growing: with polycrystal growing single-crystal in long brilliant stove, the melting zone temperature was 850 ℃ when length was brilliant, the melting zone width is about 2.5 centimetres, last ambient temperature is lower than about 60 ℃ in melting zone, following ambient temperature is then got its thermograde near 70 ℃/cm, and crystalline growth velocity is 6 millimeters/day, utilizes the effect of segregation to obtain the Hg-Cd-Te material of big component, in the material growth, use oval flat tube, use the two-way rotating technique of crystal for making crystal thermally equivalent in process of growth;
H). section: will grow good crystal and cut into slices from interior taking-up of material pipe, slice thickness is generally about 1mm;
I). thermal treatment:, handled 2 months according to the slice, thin piece (400 ℃) under the rational heat treatment temperature that densimetry filters out.
2. the method for the crystalline material of solid zone melting method growth 1-3 micron Te-Cd-Hg as claimed in claim 1 is characterized in that the material with this method preparation is used for the manufacturing of short-wave infrared mercury-cadmium tellurid detector.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97106362A CN1044497C (en) | 1997-04-07 | 1997-04-07 | Method for solid regional melting growth of 1-3 micron Te-Cd-Hg crystal material |
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|---|---|---|---|
| CN97106362A CN1044497C (en) | 1997-04-07 | 1997-04-07 | Method for solid regional melting growth of 1-3 micron Te-Cd-Hg crystal material |
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| CN1172174A true CN1172174A (en) | 1998-02-04 |
| CN1044497C CN1044497C (en) | 1999-08-04 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114481329A (en) * | 2020-10-26 | 2022-05-13 | 昆明物理研究所 | Omnidirectional multistage heating controlled tellurium-zinc-cadmium crystal growth furnace and crystal growth method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4545848A (en) * | 1982-11-08 | 1985-10-08 | Mcdonnell Douglas Corporation | HCT Crystal growth method |
| JPS61106498A (en) * | 1984-07-10 | 1986-05-24 | Yokogawa Hokushin Electric Corp | Method for growing cdte crystal |
| JPS624692A (en) * | 1985-06-28 | 1987-01-10 | Mitsubishi Heavy Ind Ltd | Method for selecting connection of combination mooring line |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114481329A (en) * | 2020-10-26 | 2022-05-13 | 昆明物理研究所 | Omnidirectional multistage heating controlled tellurium-zinc-cadmium crystal growth furnace and crystal growth method |
| CN114481329B (en) * | 2020-10-26 | 2023-11-14 | 昆明物理研究所 | Omnidirectional multi-section heating control tellurium-zinc-cadmium crystal growth furnace and crystal growth method |
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| CN1044497C (en) | 1999-08-04 |
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