阅读说明：本技术 一种用于锑化铟区域提纯的装置及方法 (Device and method for purifying indium antimonide region ) 是由 陈建才 叶薇 刘世能 李忠良 何雯瑾 杨文运 太云见 黄晖 于 2019-10-31 设计创作，主要内容包括：本发明涉及一种用于锑化铟区域提纯的装置及方法,属于光电材料技术领域。所述装置包括石英管、石英舟、背景加热带；所述背景加热带为带状电炉丝；背景加热带缠绕在石英管表面,石英舟置于密封且充有保护气体的石英管中,待提纯的锭条放在石英舟中；移动加热设备为移动加热电炉,包括保温块、电炉丝、不锈钢外壳和接线柱。所述的装置中,用多晶莫来石材料作保温块,方便加工和保温效果比石棉、耐火砖等材料好,用Φ2.5mm的oCr27A7Mo2材料的电炉丝既满足加热功率又可以长久使用,用接线柱采用瓷柱和螺丝螺纹连接并在二者之间设云母片,相比本领域现有技术中所采用的普通接头耐用,避免频繁烧坏。(The invention relates to a device and a method for purifying an indium antimonide region, and belongs to the technical field of photoelectric materials. The device comprises a quartz tube, a quartz boat and a background heating belt; the background heating belt is a belt-shaped electric furnace wire; the background heating belt is wound on the surface of the quartz tube, the quartz boat is arranged in the sealed quartz tube filled with protective gas, and the ingot to be purified is arranged in the quartz boat; the mobile heating equipment is a mobile heating electric furnace and comprises a heat preservation block, an electric furnace wire, a stainless steel shell and a binding post. In the device, polycrystal mullite material is used as a heat insulation block, the processing is convenient, the heat insulation effect is better than that of asbestos, refractory bricks and the like, the electric furnace wire made of oCr27A7Mo2 material with the diameter of 2.5mm meets the heating power and can be used for a long time, the binding post is connected with the screw thread by adopting the porcelain column and the screw, and the mica sheet is arranged between the porcelain column and the screw thread.)

1. A device for regional purification of indium antimonide, characterized in that: the device comprises a quartz tube (1), a quartz boat (2) and a background heating belt (3); the background heating belt (3) is a belt-shaped electric furnace wire; the background heating belt (3) is wound on the surface of the quartz tube (1), the quartz boat (2) is arranged in the sealed quartz tube (1) filled with protective gas, and the ingot (5) to be purified is arranged in the quartz boat (2);

the length of the area of the quartz tube (1) wound with the background heating belts (3) is greater than that of the quartz boat (2), and the distance between two adjacent background heating belts (3) on the surface of the quartz tube (1) is greater than zero;

the apparatus further comprises and a mobile heating device (4); the movable heating equipment (4) reciprocates from one end of the quartz tube (1) to the other end to heat different areas of the ingot strip (5);

four quartz tubes (1) form a group, each quartz tube (1) is 1200mm long, and the inner diameter is 80 mm;

the mobile heating equipment (4) is a mobile heating electric furnace and comprises a heat-insulating block (7), an electric furnace wire (8), a stainless steel shell and a binding post (9);

the heat insulation block (7) is two cylinders processed by a polycrystalline mullite heat insulation material, the distance between the inner diameter of the heat insulation block (7) and the outer diameter of the quartz tube (1) is 5mm, a semicircular annular groove is formed between the inner diameter and the outer diameter, and the annular groove is used for placing an electric furnace wire (8);

the diameter of the electric furnace wire (8) is 2.5mm, the material is oCr27A7Mo2, the maximum working temperature is 1400 ℃, the electric furnace wire is processed into a spiral electric furnace wire with the outer diameter of 18mm, and the heating power of each movable electric heating furnace is 700W;

the stainless steel shell is used for fixing and protecting the heat-insulating block (7), is arranged outside the heat-insulating block (7), is matched with the heat-insulating block (7) in shape, and is processed into a cylindrical cylinder by stainless steel materials;

the binding post (9) of the electric furnace is formed by connecting a screw and a porcelain column in a threaded manner, and a mica sheet (10) is arranged between the screw and the porcelain column;

a heat preservation block (7) is horizontally arranged underground, and one surface of the annular groove faces upwards; the electric furnace wire (8) is placed in the annular groove, and the other heat-insulating block (7) is placed on the annular groove, wherein one surface of the annular groove faces downwards; the heat preservation block (7) with the electric furnace wire (8) assembled is placed into a stainless steel shell to be fixed, and the electric furnace wire (8) is drawn out to be connected to a binding post (9) to form a movable heating electric furnace;

a movable heating electric furnace is sleeved outside each quartz tube (1), and the distance between the two movable heating electric furnaces is 150-160 mm;

three movable heating electric furnaces are sleeved on the outer side of each quartz tube (1), and the number of the four quartz tubes (1) is 12.

2. The apparatus of claim 1, wherein the apparatus further comprises: the inner diameter of the heat insulation block (7) is 96mm, the outer diameter is 153mm, and the thickness is 27.5 mm.

3. The apparatus of claim 1, wherein the apparatus further comprises: the distance between two adjacent background heating belts (3) on the surface of the quartz tube (1) is the width of the background heating belts (3).

4. The apparatus of claim 1, wherein the apparatus further comprises: the two ends of the quartz boat (2) are in a semi-conical shape, and the included angle between the axis of the cone and the generatrix of the cone is 22-25 degrees.

5. The apparatus of claim 1, wherein the apparatus further comprises: when the indium antimonide is subjected to regional purification, the quartz boat (2) is obliquely arranged in the quartz tube (1), and one end of the quartz boat (2) is 10-15 degrees higher than the other end.

6. The apparatus of claim 1, wherein the apparatus further comprises:

the inner diameter of the heat-insulating block (7) is 96mm, the outer diameter is 153mm, and the thickness is 27.5 mm;

the distance between two adjacent background heating belts (3) on the surface of the quartz tube (1) is the width of the background heating belts (3);

the two ends of the quartz boat (2) are in a semi-conical shape, and the included angle between the axis of the cone and the generatrix of the cone is 22-25 degrees;

when the indium antimonide is subjected to regional purification, the quartz boat (2) is obliquely arranged in the quartz tube (1), and one end of the quartz boat (2) is 10-15 degrees higher than the other end.

7. A method for zone purification of indium antimonide, characterized by: the method adopts the device for purifying the indium antimonide region as claimed in any one of claims 1 to 6, and comprises the following steps:

(1) mixing indium and antimony with the purity of 6N or 7N according to the molar ratio of 1:1, charging 2.5kg in each tube, placing the mixture in a quartz boat (2), transferring the quartz boat into a quartz tube (1) filled with hydrogen and sealed, heating to completely melt the solid in the quartz boat (2), preserving heat for 5-6 h to ensure that the antimony and the indium are uniformly mixed, and solidifying into an ingot (5) to obtain an indium antimonide polycrystalline material;

(2) putting the ingot (5) made of the indium antimonide polycrystalline material into a quartz boat (2), and then obliquely putting the quartz boat (2) in the middle of a quartz tube (1), wherein one end of the quartz boat (2) is 10-15 degrees higher than the other end; then the quartz tube (1) is vacuumized, filled with hydrogen and finally sealed;

(3) electrifying the background heating belt (3) to enable the surface temperature of the quartz tube (1) to reach 310-320 ℃, simultaneously heating the ingot strip (5) by using a movable heating device (4) from one end of the quartz tube (1), wherein the heating temperature of the movable heating device (4) is 530-540 ℃, changing the position of the movable heating device (4) after a melting zone (6) is generated on the ingot strip (5), and moving the movable heating device (4) from one end of the quartz tube (1) to the other end to finish primary purification at the moving speed of 40-50 mm/h; after 20-25 times of purification, stopping the work of the background heating belt (3) and the movable heating equipment (4), and taking out the ingot bar (5) from the quartz tube (1) after cooling to room temperature;

(4) removing the parts with high impurity content at the two ends of the ingot bar (5), and keeping the concentration N of the current carrier to be less than or equal to 1 multiplied by 10¹⁴cm^-3(77K) Electron mobility u is 5.5X 10⁵The ingot (5) part of the/V.S. (77K), this part of the ingot (5) being the regionally purified product of indium antimonide, being the starting material for the growth of single crystals of indium antimonide.

Technical Field

The invention relates to a device and a method for purifying an indium antimonide region, and belongs to the technical field of photoelectric materials.

Background

Indium antimonide is a material with the narrowest forbidden band width and the largest mobility in a III-V group compound semiconductor, has stable physical and chemical properties, and is widely applied to the aspects of infrared detectors, Hall devices and the like. The quantum efficiency of the infrared detector is closely related to the selected infrared sensitive material, indium antimonide has very high quantum efficiency in a wave band of 3-5 microns, and the indium antimonide has low cost in preparing the infrared detector, so that the indium antimonide infrared detector draws more and more attention with important application in military and wide prospect in civil. In addition, in order to adapt to the trend of large-scale development of indium antimonide infrared focal plane array devices, and meanwhile, in order to reduce the development cost of infrared detector devices and improve the production efficiency, the development of large-size indium antimonide single crystal growth technology is always researched at home and abroad.

At present, the growth of indium antimonide single crystal mainly adopts the conventional Czochralski (Czochralski) method, namely, firstly, the purchased indium and antimony are melted and solidified to prepare indium antimonide polycrystalline material, and then the indium antimonide polycrystalline material is used as raw material to prepare the indium antimonide single crystal. The purities of the purchased antimony and indium are 6N, the impurities contained in the antimony and indium and the impurities introduced in the process operation process can cause that the synthesized indium antimonide polycrystalline material contains more impurities and the distribution of the impurities is not ideal, however, the existence of the impurities has important influence on the performance of the indium antimonide single crystal, and therefore, the prepared indium antimonide polycrystalline material needs to be purified before the growth of the indium antimonide single crystal.

Generally, a region purification method is adopted to remove impurity elements in the indium antimonide polycrystalline material, and the purified indium antimonide is richThe carrier concentration N of the crystal material is less than or equal to 1 multiplied by 10¹⁴cm^-3(77K) Electron mobility u is not less than 5 x 10⁵V.S (77K). When a piece of material containing impurities is melted and then slowly solidified, the concentration of the impurities in each part of the solid is different, which is the segregation phenomenon. The zone purification also belongs to the segregation phenomenon, only a part of the ingot is melted into a melting zone in the operation process, but not the whole ingot is completely melted, then the melting zone is moved from one end of the ingot to the other end (generally, the length of the melting zone is kept unchanged), namely, one-time purification is completed, after tens of times of zone purification, p-type impurities with the distribution coefficient larger than 1 are concentrated at the head part of the ingot (namely, the zone purification passes through firstly), n-type impurities with the distribution coefficient smaller than 1 are concentrated at the tail part of the ingot (namely, the zone purification passes through last), and the p-type and n-type impurities in the middle part of the ingot are low in content, so that the part with high impurity concentration is removed, and the part with low impurity concentration is reserved, thereby achieving the purpose of purification.

Disclosure of Invention

Aiming at the defects in the prior art, the invention aims to provide a device and a method for indium antimonide regional purification, aiming at improving the quality of indium antimonide raw materials, the utilization rate of the materials and the productivity, the device and the method can greatly improve the productivity, and the purified materials can meet the requirement of growing 4-5-inch indium antimonide crystal ingots.

The purpose of the invention is realized by the following technical scheme.

A device for purifying an indium antimonide area comprises a quartz tube, a quartz boat and a background heating belt; the background heating belt is a belt-shaped electric furnace wire; the background heating belt is wound on the surface of the quartz tube, the quartz boat is arranged in the sealed quartz tube filled with protective gas, and the ingot to be purified is arranged in the quartz boat.

The length of the quartz tube area wound with the background heating belts is larger than that of the quartz boat, and the distance between two adjacent background heating belts on the surface of the quartz tube is larger than zero.

The apparatus further comprises and a mobile heating device; the movable heating equipment reciprocates from one end of the quartz tube to the other end of the quartz tube to heat different areas of the ingot;

wherein, four quartz tubes are arranged to form a group, each quartz tube is 1200mm long, and the inner diameter is 80 mm.

The mobile heating equipment is a mobile heating electric furnace and comprises a heat preservation block, an electric furnace wire, a stainless steel shell and a binding post.

The heat preservation block is two cylinders processed by polycrystalline mullite heat preservation material, the distance between the inner diameter of the heat preservation block and the outer diameter of the quartz tube is 5mm, a semicircular annular groove is arranged between the inner diameter and the outer diameter, and the groove is used for placing an electric furnace wire.

Preferably, the thermal insulating block has an inner diameter of 96mm, an outer diameter of 153mm and a thickness of 27.5 mm.

The diameter of the electric furnace wire is 2.5mm, the material is oCr27A7Mo2, the maximum working temperature is 1400 ℃, and the electric furnace wire is processed into a spiral electric furnace wire with the outer diameter of 18mm, and the heating power of each small electric furnace is 700W.

A stainless steel shell: the heat-insulating block is used for fixing and protecting the heat-insulating block, is arranged outside the heat-insulating block, is matched with the heat-insulating block in shape, and is processed into a cylindrical cylinder by stainless steel materials.

The binding post of the electric furnace is formed by connecting a screw and a porcelain column in a threaded manner, and a mica sheet is arranged between the screw and the porcelain column.

One heat preservation block is horizontally placed underground, and one surface of the annular groove faces upwards; putting the electric furnace wire into the annular groove, and then putting the other heat preservation block on the annular groove, wherein one surface of the annular groove faces downwards; and (3) putting the heat preservation block with the assembled electric furnace wire into a stainless steel shell for fixing, and drawing out the electric furnace wire to connect to a binding post to form the mobile electric heating furnace.

The outer side of each quartz tube is sleeved with a movable heating electric furnace, and the distance between the two movable heating electric furnaces is 150 mm-160 mm. Three movable heating electric furnaces are sleeved outside each quartz tube, and the number of the movable heating electric furnaces of the four quartz tubes is 12.

Preferably, the distance between two adjacent background heating bands on the surface of the quartz tube (1) is the width of the background heating band (3);

preferably, the two ends of the quartz boat are in a semi-conical shape, and the included angle between the axis of the cone and the generatrix of the cone is 22-25 degrees.

When the zone purification is preferably carried out on the indium antimonide, the quartz boat is obliquely placed in the quartz tube, and one end of the quartz boat is 10-15 degrees higher than the other end of the quartz boat.

A method for regional purification of indium antimonide, the device adopted by the method is the device for regional purification of indium antimonide, and the steps are as follows:

(1) mixing indium and antimony with the purity of 6N or 7N according to the molar ratio of 1:1, charging 2.5kg in each tube, placing the mixture in a quartz boat, transferring the quartz boat into a sealed quartz tube filled with hydrogen, heating to completely melt the solid in the quartz boat, keeping the temperature for 5-6 h to ensure that the antimony and the indium are uniformly mixed, and solidifying into an ingot bar to obtain an indium antimonide polycrystalline material;

(2) putting the ingot of the indium antimonide polycrystalline material into a quartz boat, and then obliquely putting the quartz boat in the middle of a quartz tube, wherein one end of the quartz boat is 10-15 degrees higher than the other end of the quartz boat; then vacuumizing the quartz tube, filling hydrogen, and finally sealing;

(3) electrifying the background heating belt to enable the surface temperature of the quartz tube to reach 310-320 ℃, simultaneously heating the ingot strip by using a movable heating device from one end of the quartz tube, wherein the heating temperature of the movable heating device is 530-540 ℃, changing the position of the movable heating device after a melting zone is generated on the ingot strip, and moving the movable heating device from one end of the quartz tube to the other end to finish primary purification at the moving speed of 40-50 mm/h; after 20-25 times of purification, stopping the work of the background heating belt and the movable heating equipment, and taking out the ingot from the quartz tube after cooling to room temperature;

(4) removing the impurity-containing parts at two ends of the ingot bar, and keeping the carrier concentration N less than or equal to 1 × 10¹⁴cm^-3(77K) Electron mobility u is 5.5X 10⁵The V.S (77K) ingot part is a regional purified product of indium antimonide and is a raw material for growing indium antimonide single crystals.

Advantageous effects

The invention provides a device for purifying an indium antimonide region, wherein a polycrystalline mullite material is used as a heat insulation block, the device is convenient to process and has better heat insulation effect than asbestos, refractory bricks and other materials, an electric furnace wire made of r27A7Mo2 material with the temperature of phi 2.5mm meets the heating power and can be used for a long time, a binding post is connected with a porcelain column and a screw thread, and a mica sheet is arranged between the porcelain column and the screw thread.

Drawings

FIG. 1 is a schematic structural view of a heat-insulating block in the embodiment.

Fig. 2 is a schematic structural diagram of the external shape of the heating wire in the embodiment.

Fig. 3 is a schematic structural diagram of the appearance of the porcelain column in the embodiment.

FIG. 4 is a schematic structural diagram of an apparatus for zone purification of indium antimonide in the example.

The method comprises the following steps of 1-quartz tube, 2-quartz boat, 3-background heating belt, 4-mobile heating equipment, 5-ingot bar, 6-melting zone, 7-heat preservation block, 8-electric furnace wire, 9-binding post and 10-mica sheet

Detailed Description

The invention is described in detail below with reference to the drawings and specific examples, but the invention is not limited thereto.