阅读说明：本技术 一种Zn-P-As单晶的制备方法 (Preparation method of Zn-P-As single crystal ) 是由 梁彦杰 刘振兴 柴立元 杨志辉 彭聪 周元 周艺伟 邓方杰 丁风华 廖艺 于 2021-07-07 设计创作，主要内容包括：本发明公开了一种Zn-P-As单晶的制备方法,单质As与单质P放置处定义为a端,与a端相对应的用于结晶的另一端定义为c端,a端和c端之间的ZnO放置处定义为b端；保护性气氛或真空的密闭环境下,将单质As、单质P和ZnO按位置放好后,控制a端温度为870℃～890℃,c端温度为810℃～830℃,经保温晶体生长得到Zn-P-As单晶。本发明得到一种新型半导体单晶材料,具有与化学计量比为3:5:2.6的Zn-3P-5As-(2.6)晶体材料一致的结构,正交晶系,空间群为Cmcm；与单晶Si(E-g:1.1～1.3eV)的带隙接近,在新型电子器件以及光伏领域具有潜在的应用前景。(The invention discloses a preparation method of a Zn-P-As single crystal, wherein the placement position of a simple substance As and a simple substance P is defined As an a end, the other end which corresponds to the a end and is used for crystallization is defined As a c end, and the placement position of ZnO between the a end and the c end is defined As a b end; under protective atmosphere or vacuum closed environment, after putting single As, single P and ZnO according to positions, controlling the temperature of the a end to be 870-890 ℃, the temperature of the c end to be 810-830 ℃, and growing a heat-preservation crystal to obtain the Zn-P-As single crystal. The invention provides a novel semiconductor single crystal material with Zn in a stoichiometric ratio of 3:5:2.6 3 P 5 As 2.6 The crystal material has a consistent structure, an orthorhombic system and a space group of Ccm; with single crystal Si (E) g 1.1-1.3 eV), and has potential application prospect in the fields of novel electronic devices and photovoltaics.)

1. A preparation method of Zn-P-As single crystal is characterized by comprising the following steps: the place where the simple substance As and the simple substance P are placed is defined As an a end, the other end, corresponding to the a end, for crystallization is defined As a c end, and the place where ZnO between the a end and the c end is placed is defined As a b end;

under protective atmosphere or vacuum closed environment, after putting single As, single P and ZnO according to positions, controlling the temperature of the a end to be 870-890 ℃, the temperature of the c end to be 810-830 ℃, and growing a heat-preservation crystal to obtain the Zn-P-As single crystal.

2. The method for producing a Zn-P-As single crystal according to claim 1, wherein: the protective atmosphere is argon or nitrogen.

3. The method for producing a Zn-P-As single crystal according to claim 1, wherein: the ZnO is a block or is obtained by pressing ZnO powder into a sheet.

4. The method for producing a Zn-P-As single crystal according to claim 1, wherein: the molar ratio of the simple substance As to the simple substance P is 1 (0.9-1.2); the molar ratio of the simple substance As to Zn in the ZnO is 1: 0.5-2.

5. The method for producing a Zn-P-As single crystal according to claim 4, wherein: the molar ratio of the simple substance As to Zn in the ZnO is 1: 0.5-0.6.

6. The method for producing a Zn-P-As single crystal according to any one of claims 1 to 5, characterized in that: after the simple substance As, the simple substance P and the ZnO are put well according to positions, an additive is added, wherein the additive is the simple substance iodine (I)₂)、AsI₃、ZnI₂Or PI₃。

7. The method for producing a Zn-P-As single crystal according to claim 6, wherein: the addition amount of the additive is 0.05 g-2.0 g/L.

8. The method for producing a Zn-P-As single crystal according to claim 6, wherein: the growth time of the heat-preservation crystal is not less than 1 day.

Technical Field

The invention belongs to the technical field of metallurgy technology and material science and engineering, and relates to a preparation method of a novel semiconductor Zn-P-As single crystal.

Background

The arsenic compound has unique physical properties, for example, GaAs single crystal which is applied in large scale has high carrier mobility and is applied to a high-speed response computing component and a high-frequency emission electronic device, the InAs single crystal which is popularized and used has excellent photoelectric property and is used for manufacturing a photodiode, the BAS single crystal has ultrahigh thermal conductivity and is expected to become a candidate crystal of a new generation of ultrahigh-speed computing electronic device, B₁₃As₂The crystal has potential photoelectric application potential, and the CrAs single crystal has pressure-induced superconductivity and the like, so that the application of arsenide becomes an important way for exploring novel application functional materials.

Disclosure of Invention

The invention provides a preparation method of a Zn-P-As single crystal, and a novel semiconductor single crystal material is obtained, wherein the novel semiconductor single crystal material contains Zn with the stoichiometric ratio of 3:5:2.6₃P₅As_2.6Crystalline material (unit cell parameter of A structure in which α ═ β ═ γ ═ 90 °) is uniform, the crystal system is orthorhombic, and the space group is Cmcm; with single crystal Si (E)_g1.1-1.3 eV), and has potential application prospect in the fields of novel electronic devices and photovoltaics.

The invention adopts the following technical scheme:

a preparation method of Zn-P-As single crystal comprises the following steps that a place where elemental As and elemental P are placed is defined As an a end, the other end, corresponding to the a end, for crystallization is defined As a c end, and a place where ZnO between the a end and the c end is placed is defined As a b end;

under protective atmosphere or vacuum closed environment, after putting single As, single P and ZnO according to positions, controlling the temperature of the a end to be 870-890 ℃, the temperature of the c end to be 810-830 ℃, and growing a heat-preservation crystal to obtain the Zn-P-As single crystal.

Preferably, the protective atmosphere is an argon or nitrogen atmosphere.

Preferably, the ZnO is a block or obtained by pressing ZnO powder into a sheet.

Preferably, the molar ratio of the simple substance As to the simple substance P is 1 (0.9-1.2); the molar ratio of the simple substance As to Zn in the ZnO is 1: 0.5-2; preferably, the molar ratio of the simple substance As to the Zn in the ZnO is 1: 0.5-0.6.

Preferably, after the simple substance As, the simple substance P and the ZnO are put well according to positions, the additive is added, and the additive is the simple substance iodine (I)₂)、AsI₃、ZnI₂Or PI₃. The invention can accelerate the transmission of gas phase substances and improve the growth speed of crystals by adding the additive.

More preferably, the addition amount of the additive is 0.05g to 2.0 g/L.

Preferably, the growth time of the heat-preservation crystal is not less than 1 day, and millimeter-scale crystals can be obtained.

According to the invention, ZnO is used As a Zn source, powder ZnO is tableted or bulk ZnO is directly adopted, so that the excessively fast gas phase migration of the Zn source can be inhibited, and the growth of the Zn-P-As single crystal can be controllably realized.

The invention adopts ZnO as Zn source to control the migration rate of the Zn source, and the ZnO → Zn passes through under the action of P at high temperature₃(PO₄)₂So As to realize the transfer of partial Zn and synthesize Zn-P-As crystals at the crystallization end.

The invention prepares a novel semiconductor Zn-P-As single crystal material which has Zn in a stoichiometric ratio of 3:5:2.6₃P₅As_2.6Crystalline material (unit cell parameter of A structure in which α ═ β ═ γ ═ 90 °) is uniform, the crystal system is orthorhombic, and the space group is Cmcm; with single crystal Si (E)_g1.1-1.3 eV), and has potential application prospect in the fields of novel electronic devices and photovoltaics.

The crystal prepared by the invention has millimeter-scale single crystal characteristics, can be used as seed crystal for large-scale crystal growth, and is beneficial to large-scale preparation and popularization of novel crystals.

Drawings

FIG. 1 is a schematic view showing the growth of a single crystal of Zn-P-As;

FIG. 2 shows structural analysis information of the single crystal obtained in example 2.

FIG. 3 is the phase analysis result and the morphology photograph of the crystals grown in examples 1 to 5 (the inset is an optical picture, and the grid paper is 1mmx1 mm).

FIG. 4 shows the results of optical property tests of the crystal in example 2.

Detailed Description

To illustrate the characteristics of the present invention, the present invention is described with reference to examples, which use a high purity quartz tube as a container, an inner diameter of 16mm, a wall thickness of 1.5mm, a reaction chamber length of about 15cm after sealing by melting, and perform sampling and preparation of ingredients in an argon-protected glove box (normal pressure, water content <1ppm, oxygen content <1ppm), and finally perform sealing by using oxyhydrogen flame.

It should be noted that the relative distances among the ends a, b and c of the high purity quartz tube in the embodiment can be adjusted according to actual conditions as long as the relative positions are not changed.

Example 1

Weighing 0.315g of simple substance As, 0.135g of simple substance P and 0.200g of zinc oxide powder ZnO, tabletting the ZnO powder, placing according to the figure 1, adding 0.0265g of simple substance iodine, and sealing the tube in vacuum. And then, placing the quartz tube in a reaction furnace, heating to 880 ℃ at the end a and 820 ℃ at the end c, carrying out heat preservation growth, carrying out heat preservation for 1 day, cooling to room temperature, taking out the grown single crystal, grinding part of the single crystal, and carrying out phase identification.

Example 2

0.315g of elemental As, 0.136g of elemental P and 0.202g of zinc oxide sheet are weighed, placed according to the figure 1, added with 0.0265g of elemental iodine, and subjected to vacuum tube sealing. And then, placing the quartz tube in a reaction furnace, heating to 880 ℃ at the end a and 820 ℃ at the end c, carrying out heat preservation growth, carrying out heat preservation for 1 day, cooling to room temperature, taking out the grown single crystal, carrying out single crystal XRD detection, grinding part of the single crystal, and carrying out phase identification.

As shown in FIG. 2, the single crystal was Zn according to the structural analysis₃P₅As_2.6。

As shown in FIG. 4, Zn₃P₅As_2.6The optical band gap of the crystal is about 1.2 eV.

Example 3

Weighing 0.321g of simple substance As, 0.135g of simple substance P and 0.212g of zinc oxide powder ZnO, tabletting the zinc oxide powder, placing according to the figure 1, adding 0.0984g of simple substance iodine, and sealing the tube in vacuum. And then, placing the quartz tube in a reaction furnace, heating to 880 ℃ at the end a and 820 ℃ at the end c, carrying out heat preservation growth, carrying out heat preservation for 1 day, cooling to room temperature, taking out the grown single crystal, grinding part of the single crystal, and carrying out phase identification.

Example 4

Weighing 0.314g of elemental As, 0.134g of elemental P and 0.308g of zinc oxide sheet ZnO, placing according to the figure 1, adding 0.0265g of elemental iodine, and sealing the tube in vacuum. And then, placing the quartz tube in a reaction furnace, heating to 880 ℃ at the end a and 820 ℃ at the end c, carrying out heat preservation growth, carrying out heat preservation for 7 days, cooling to room temperature, taking out the grown single crystal, grinding part of the single crystal, and carrying out phase identification.

Example 5

Weighing 0.310g of simple substance As, 0.136g of simple substance P and 0.252g of zinc oxide sheet ZnO, placing according to the figure 1, adding 0.0265g of simple substance iodine, and sealing the tube in vacuum. And then, placing the quartz tube in a reaction furnace, heating to 880 ℃ at the end a and 820 ℃ at the end c, carrying out heat preservation growth, carrying out heat preservation for 7 days, cooling to room temperature, taking out the grown single crystal, grinding part of the single crystal, and carrying out phase identification.