阅读说明：本技术 化合物砷酸碲锌铅和砷酸碲锌铅非线性光学晶体及制备方法和用途 (Compound arsenic acid tellurium zinc lead and arsenic acid tellurium zinc lead nonlinear optical crystal and preparation method and purposes ) 是由 俞洪伟 钱震 吴红萍 于 2019-08-27 设计创作，主要内容包括：化合物砷酸碲锌铅及砷酸碲锌铅非线性光学晶体的制备方法和用途,化合物砷酸碲锌铅及砷酸碲锌铅非线性光学晶体化学式均为Pb<Sub>3</Sub>Zn<Sub>3</Sub>TeAs<Sub>2</Sub>O<Sub>14</Sub>,晶体属三方晶系,空间群P321,晶胞参数为<Image he="56" wi="290" file="DDA0002180303900000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image><Image he="43" wi="700" file="DDA0002180303900000012.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>分子量1319.2,其粉末倍频效应约为3倍KDP(KH<Sub>2</Sub>PO<Sub>4</Sub>)。化合物砷酸碲锌铅采用固相反应法合成,砷酸碲锌铅非线性光学晶体采用高温熔液法或者提拉法生长,该砷酸碲锌铅非线性光学晶体机械硬度大,易于切割、抛光加工和保存,在制备倍频发生器、上频率转换器、下频率转换器或光参量振荡器等非线性光学器件中得到广泛应用。(The preparation method and purposes of compound arsenic acid tellurium zinc lead and arsenic acid tellurium zinc lead nonlinear optical crystal, compound arsenic acid tellurium zinc lead and arsenic acid tellurium zinc lead nonlinear optical crystal chemical formula are Pb 3 Zn 3 TeAs 2 O 14 , crystal category trigonal system, space group P321, cell parameter is Molecular weight 1319.2, powder SHG effect are about 3 times of KDP (KH 2 PO 4 ).Compound arsenic acid tellurium zinc lead is synthesized using solid reaction process, arsenic acid tellurium zinc lead nonlinear optical crystal uses high temperature solution method or Czochralski grown, the arsenic acid tellurium zinc lead nonlinear optical crystal mechanical hardness is big, easy to cut, polishing and preservation are used widely in the device for non-linear optical such as preparation times frequency generator, upper frequency converter, lower frequency converter or optical parametric oscillator.)

1. compound arsenic acid tellurium zinc lead, which is characterized in that the compound arsenic acid tellurium zinc lead chemical formula is Pb₃Zn₃TeAs₂O₁₄。

2. the preparation method of compound arsenic acid tellurium zinc lead according to claim 1, which comprises the following steps: The compound is made using solid reaction process by lead-containing compounds, zinc compound, containing tellurium compound, arsenical mixing Arsenic acid tellurium zinc lead, wherein Element Lead in lead-containing compounds, element zinc in zinc compound, containing elemental tellurium in tellurium compound, contain arsenic The molar ratio of element arsenic is 3:3:1:2 in compound.

3. the preparation method of compound arsenic acid tellurium zinc lead described in claim 2, which is characterized in that the compound arsenic acid tellurium zinc lead It is prepared using solid reaction process, process includes: by lead-containing compounds, zinc compound, containing tellurium compound, arsenical raw material It is uniformly mixed, is put into Muffle furnace after grinding, pre-burning excludes the moisture and gas in raw material, is cooled to room temperature, and takes out grinding After be put into Muffle furnace and calcine, compound arsenic acid tellurium zinc lead is made；

The lead-containing compounds include at least one of ceruse, plumbi nitras, lead oxide, lead acetate or lead oxalate；

The zinc compound includes at least one of zinc nitrate, zinc oxide, zinc carbonate or zinc acetate；

The tellurium compound that contains is at least one of tellurium dioxide, telluric acid anhydride, telluric acid, tellurous acid；

The arsenide includes at least one of diarsenic pentoxide or arsenate (arsenic acid, arsenic acid, pyroarsenic acid).

4. arsenic acid tellurium zinc lead nonlinear optical crystal, which is characterized in that the chemical formula of the crystal is Pb₃Zn₃TeAs₂O₁₄, molecular weight 1319.2, do not have symmetrical centre, belong to trigonal system, space group P321, cell parameter is

5. the preparation method of arsenic acid tellurium zinc lead nonlinear optical crystal as claimed in claim 4, which is characterized in that use high temperature melting Liquid method or Czochralski grown arsenic acid tellurium zinc lead nonlinear optical crystal.

6. method according to claim 5, which is characterized in that the arsenic acid tellurium zinc lead nonlinear optical crystal uses high temperature melting Liquid method or czochralski method preparation, process include:

A, by any resulting compound arsenic acid tellurium zinc lead single-phase polycrystalline powder of claim 1-3 or any institute of claim 1-3 The mixture of the compound arsenic acid tellurium zinc lead single-phase polycrystalline powder and fluxing agent that obtain, is warming up to fusing and obtains mixed molten liquid；

Or directly by lead-containing compounds, zinc compound and containing tellurium compound, the mixture of arsenical or lead-containing compounds, Zinc compound, the mixture containing tellurium compound and arsenical and fluxing agent, are warming up to fusing and obtain mixed molten liquid；

B, it fills in the corundum crucible merging crystal growing furnace of mixed molten liquid made from step a, seed crystal is fixed on seed rod, Seed crystal is subjected to melt back in contact mixed molten liquid liquid level or mixed molten liquid, is down to saturation temperature；Cooling or constant temperature growth, system Standby arsenic acid tellurium zinc lead nonlinear optical crystal out.

7. method according to claim 6, it is characterised in that wherein compound arsenic acid tellurium zinc lead single-phase polycrystalline powder with it is fluxing The molar ratio of agent is 1:0-20；Or wherein lead-containing compounds, zinc compound, containing tellurium compound and arsenical with it is fluxing The molar ratio of agent is 3:3:1:2:0-20；Fluxing agent includes lead oxide, zinc oxide, tellurium dioxide, telluric acid, diarsenic pentoxide, arsenic At least one of acid, composite fluxing agent include one of following or a variety of:

PbO-TeO₂、PbO-H₆TeO₆、PbO-TeO₂-As₂O₅、PbO-H₆TeO₆-H₃AsO₄·1/2H₂O、PbO-As₂O₅、PbO- H₃AsO₄·1/2H₂O、ZnO-TeO₂、ZnO-H₆TeO₆、ZnO-TeO₂-As₂O₅、ZnO-H₆TeO₆-As₂O₅、ZnO-As₂O₅、ZnO- H₃AsO₄·1/2H₂O、PbO-ZnO、PbO-ZnO-TeO₂、PbO-ZnO-H₆TeO₆、PbO-ZnO-As₂O₅、PbO-ZnO- H₃AsO₄·1/2H₂O etc..

8. method according to claim 7, which is characterized in that composite fluxing agent PbO-TeO₂PbO and TeO in system₂Mole Than for 1-3:2-5；PbO-H₆TeO₆PbO and H in system₆TeO₆Molar ratio is 1-3:3-6；PbO-TeO₂-As₂O₅PbO in system, TeO₂With As₂O₅Molar ratio is 1-3:2-5:2-6；PbO-H₆TeO₆-H₃AsO₄·1/2H₂PbO, H in O system₆TeO₆With H₃AsO₄·1/2H₂O molar ratio is 1-3:2-5:1-6；PbO-As₂O₅PbO and As in system₂O₅Molar ratio be 1-3:2-5； PbO-H₃AsO₄·1/2H₂PbO and H in O system₃AsO₄·1/2H₂The molar ratio of O is 1-3:2-5；ZnO-TeO₂ZnO in system With TeO₂Molar ratio be 1-5:2-5；ZnO-H₆TeO₆ZnO and H in system₆TeO₆Molar ratio be 1-6:2-5；ZnO-TeO₂- As₂O₅ZnO, TeO in system₂With As₂O₅Molar ratio is 1-5:2-6:1-6；ZnO-H₆TeO₆-As₂O₅ZnO, H in system₆TeO₆With TeO₂Molar ratio is 1-5:2-5:2-6；ZnO-As₂O₅ZnO and As in system₂O₅Molar ratio is 1-3:3-6；ZnO-H₃AsO₄·1/ 2H₂ZnO and H in O system₃AsO₄·1/2H₂O molar ratio is 1-3:3-6；PbO and ZnO molar ratio are 1-3 in PbO-ZnO system: 1-3；PbO-ZnO-TeO₂PbO, ZnO and TeO in system₂Molar ratio is 1-3:1-3:3-6；PbO-ZnO-H₆TeO₆In system PbO, ZnO and H₆TeO₆Molar ratio is 1-3:1-3:3-6；PbO-ZnO-As₂O₅PbO, ZnO and As in system₂O₅Molar ratio is 1- 3:1-3:2-5；PbO-ZnO-H₃AsO₄·1/2H₂PbO, ZnO and H in O system₃AsO₄·1/2H₂O molar ratio is 1-3:1-3:3- 6。

9. the purposes of arsenic acid tellurium zinc lead nonlinear optical crystal according to claim 4, which is characterized in that the arsenic acid tellurium zinc Lead nonlinear optical crystal is used to prepare a times frequency generator, upper frequency converter, lower frequency converter or optical parametric oscillator.

Technical field

It is Pb the present invention relates to chemical formula₃Zn₃TeAs₂O₁₄Compound arsenic acid tellurium zinc lead and arsenic acid tellurium zinc lead nonlinear optical Learn crystal, the preparation method of crystal and the device for non-linear optical using crystal production.

Background technique

It is big, brilliant through wide waveband, light injury threshold is big, physical and chemical performance is stable novel non-linearity optics to explore frequency-doubled effect Body is always the hot topic in laser frequency field.Predominant non-linearity optical material has at present: β-BaB₂O₄(BBO) crystal, LiB₃O₅(LBO) crystal, CsB₃O₅(CBO) crystal, CsLiB₆O₁₀(CLBO) crystal and KBe₂BO₃F₂(KBBF) crystal.Although this The crystal technique of a little materials has reached its maturity, but there are still clearly disadvantageous places: as crystal easily deliquesces, growth cycle Long, layer growth habit is serious and expensive etc..Therefore, find new non-linear optical crystal material be still one very Important and large order.For the deficiency for making up the above nonlinear optical crystal, scientists from all over the world, which are still in, strongly to be paid close attention to respectively The optical property and mechanical performance of crystal are not only focused in the exploration and research of class novel nonlinear optical crystal, but also increasingly Pay attention to the preparation characteristic of crystal.

Arsenic acid salt crystal is important semiconductor material, middle infrared material, and performance is widely paid close attention to, and leads in optics There is relatively broad application in the fields such as domain, military exploration and laser medicine.Since its band gap is larger, laser damage threshold is higher, Physical and chemical performance is stablized, and is conducive to obtain stronger nonlinear optical effect, is the ideal choosing of novel middle infrared nonlinear optical crystal It selects.

Summary of the invention

It is an object of that present invention to provide compound arsenic acid tellurium zinc lead and arsenic acid tellurium zinc lead nonlinear optical crystal, chemical formula are equal For Pb₃Zn₃TeAs₂O₁₄；

Another object of the present invention, which is to provide, synthesizes compound arsenic acid tellurium zinc lead and high temperature solution method using solid reaction process Or the preparation method of Czochralski grown arsenic acid tellurium zinc lead nonlinear optical crystal；

Further object of the present invention is to provide the purposes of arsenic acid tellurium zinc lead device for non-linear optical, is used to prepare frequency multiplication Device, up or down frequency converter or optical parametric oscillator.

Technical scheme is as follows:

Compound arsenic acid tellurium zinc lead provided by the invention, chemical formula Pb₃Zn₃TeAs₂O₁₄；Preparation process includes: that will contain Lead compound, zinc compound are uniformly mixed containing tellurium compound, arsenical raw material, are put into Muffle furnace after grinding, pre-burning The moisture and gas in raw material are excluded, is cooled to room temperature, takes out to be put into Muffle furnace after grinding and calcine, compound arsenic acid is made Tellurium zinc lead；

The lead-containing compounds include at least one of ceruse, plumbi nitras, lead oxide, lead acetate or lead oxalate；

The zinc compound includes at least one of zinc nitrate, zinc carbonate, zinc oxide or zinc acetate；

The tellurium compound that contains is at least one of tellurium dioxide, telluric acid anhydride, telluric acid, tellurous acid；

The arsenide includes at least one of diarsenic pentoxide or arsenate (arsenic acid, arsenious acid, pyroarsenic acid)；

It uses solid reaction process that can prepare arsenic acid tellurium zinc lead compound by following chemical equation:

1)3PbO+3ZnO+H₆TeO₆+As₂O₅→Pb₃Zn₃TeAs₂O₁₄+3H₂O↑

2)3PbCO₃+3ZnO+H₆TeO₆+As₂O₅→Pb₃Zn₃TeAs₂O₁₄+3CO₂↑+3H₂O↑

3)6Pb(NO₃)₂+6ZnO+2H₆TeO₆+2As₂O₅→2Pb₃Zn₃TeAs₂O₁₄+12NO₂↑+6H₂O↑+3O₂↑

4)6PbO+6ZnO+2TeO₂+2As₂O₅+O₂→2Pb₃Zn₃TeAs₂O₁₄

5)6PbCO₃+6ZnO+2TeO₂+2As₂O₅+O₂→2Pb₃Zn₃TeAs₂O₁₄+6CO₂↑

6)3Pb(NO₃)₂+3ZnO+TeO₂+As₂O₅→Pb₃Zn₃TeAs₂O₁₄+6NO₂↑+O₂↑

7)6PbO+6Zn(NO₃)₂+2H₆TeO₆+2As₂O₅→2Pb₃Zn₃TeAs₂O₁₄+6H₂O↑+12NO₂↑+3O₂↑

8)3PbO+3Zn(NO₃)₂+TeO₂+As₂O₅→Pb₃Zn₃TeAs₂O₁₄+6NO₂↑+O₂↑

9)3PbO+3ZnO+H₆TeO₆+2H₃AsO₄·1/2H₂O→Pb₃Zn₃TeAs₂O₁₄+7H₂O↑

10)3PbCO₃+3ZnO+H₆TeO₆+2H₃AsO₄·1/2H₂O→Pb₃Zn₃TeAs₂O₁₄+3CO₂↑+7H₂O↑

11)6Pb(NO₃)₂+6ZnO+2H₆TeO₆+4H₃AsO₄·1/2H₂O→2Pb₃Zn₃TeAs₂O₁₄+12NO₂↑+14H₂O↑+ 3O₂↑

12)6PbO+6ZnO+2TeO₂+4H₃AsO₄·1/2H₂O+O₂→2Pb₃Zn₃TeAs₂O₁₄+8H₂O↑

13)6PbO+6Zn(NO₃)₂+2H₆TeO₆+4H₃AsO₄·1/2H₂O→2Pb₃Zn₃TeAs₂O₁₄+14H₂O↑+12NO₂↑+ 7O₂↑

14)3PbO+3Zn(NO₃)₂+TeO₂+2H₃AsO₄·1/2H₂O→Pb₃Zn₃TeAs₂O₁₄+6NO₂↑+4H₂O↑+O₂↑

Arsenic acid tellurium zinc lead nonlinear optical crystal provided by the invention, it is characterised in that the chemical formula of the crystal is Pb₃Zn₃TeAs₂O₁₄, molecular weight 1319.2 do not have symmetrical centre, belongs to trigonal system, space group P321, cell parameter is Its powder SHG effect About 3 times of KDP (KH₂PO₄)。

The preparation method of arsenic acid tellurium zinc lead nonlinear optical crystal provided by the invention, using high temperature solution method or lifting Method grows arsenic acid tellurium zinc lead nonlinear optical crystal, and concrete operations follow these steps to carry out:

A, compound arsenic acid tellurium zinc lead single-phase polycrystalline powder is uniformly mixed with fluxing agent, with the heating of 1-30 DEG C/h of temperature Rate is heated to 650-1000 DEG C of temperature, constant temperature 5-80 hours, obtains mixed molten liquid, then be cooled to 500-800 DEG C of temperature, Wherein the molar ratio of compound arsenic acid tellurium zinc lead single-phase polycrystalline powder and fluxing agent is 1:0-20；

Or directly by lead-containing compounds, zinc compound, the mixture containing tellurium compound and arsenical or contain leaded The mixture of object, zinc compound, the mixture containing tellurium compound and arsenical and fluxing agent is closed, with 1-30 DEG C/h of temperature Heating rate be heated to 650-1000 DEG C of temperature, constant temperature 5-80 hours, obtain mixed molten liquid, then be cooled to temperature 500- 800 DEG C, wherein lead-containing compounds, zinc compound, the mixture containing tellurium compound and arsenical and fluxing agent mole Than for 3:3:1:2:0-20；

The fluxing agent mainly has from fluxing agent, such as PbO, TeO₂、As₂O₅、H₆TeO₆、H₃AsO₄·1/2H₂O、PbF₂、 H₂TeO₃、Pb(NO₃)₂Deng and other composite fluxing agents, such as PbO-TeO₂、PbO-H₆TeO₆、PbO-TeO₂-As₂O₅、PbO- H₆TeO₆-H₃AsO₄·1/2H₂O、PbO-As₂O₅、PbO-H₃AsO₄·1/2H₂O、ZnO-TeO₂、ZnO-H₆TeO₆、ZnO-TeO₂- As₂O₅、ZnO-H₆TeO₆-As₂O₅、ZnO-As₂O₅、ZnO-H₃AsO₄·1/2H₂O、PbO-ZnO、PbO-ZnO-TeO₂、PbO-ZnO- H₆TeO₆、PbO-ZnO-H₃AsO₄·1/2H₂O、PbO-ZnO-As₂O₅Deng.

The compound arsenic acid tellurium zinc lead single-phase polycrystalline powder is prepared using solid-phase synthesis, comprising the following steps: will be contained The compound arsenic is made using solid reaction process containing tellurium compound and arsenical mixing in lead compound, zinc compound Sour tellurium zinc lead, Element Lead in lead-containing compounds, element zinc in zinc compound, containing elemental tellurium, arsenical in tellurium compound The molar ratio of middle element arsenic is 3:3:1:2, by lead-containing compounds, zinc compound, contains tellurium compound and arsenical raw material It is uniformly mixed, is put into Muffle furnace after grinding, pre-burning excludes the moisture and gas in raw material, is cooled to room temperature, and takes out grinding After be put into Muffle furnace and calcine, be warming up to 600-900 DEG C, constant temperature 72 hours, be cooled to room temperature, take out ground obtained compound Arsenic acid tellurium zinc lead single-phase polycrystalline powder.

B, prepare arsenic acid tellurium zinc lead seed crystal: the mixed molten liquid that step a is obtained slowly is dropped with the rate of 0.5-10 DEG C/h of temperature To room temperature, spontaneous crystallization obtains arsenic acid tellurium zinc lead seed crystal；

C, step a will be filled to be made in the crucible merging crystal growing furnace of mixed molten liquid, the obtained seed crystal of step b is fixed In on seed rod, from the lower seed crystal in crystal growing furnace top, first preheat seed crystal 5-60 minutes, by seed crystal down toward contact mixed molten liquid liquid Melt back is carried out in face or mixed molten liquid, and constant temperature 5-60 minutes, saturation temperature is down to the rate of 1-60 DEG C/h of temperature；

D, again with 0.1-5 DEG C/day of temperature of rate slow cooling, crystal is carried out with 0-60rpm revolving speed rotary seed crystal rod Growth, after crystal growth to required scale, is down to room by crystal lift-off mixed molten liquid surface, and with temperature 1-80 DEG C/h rate Then temperature is taken out crystal from burner hearth, arsenic acid tellurium zinc lead nonlinear optical crystal can be obtained.

The fluxing agent PbO-TeO₂PbO and TeO in system₂Molar ratio be 1-3:2-5；PbO-H₆TeO₆PbO in system With H₆TeO₆Molar ratio is 1-3:3-6；PbO-TeO₂-As₂O₅PbO, TeO in system₂With As₂O₅Molar ratio is 1-3:2-5:2-6； PbO-H₆TeO₆-H₃AsO₄·1/2H₂PbO, H in O system₆TeO₆With H₃AsO₄·1/2H₂O molar ratio is 1-3:2-5:1-6； PbO-As₂O₅PbO and As in system₂O₅Molar ratio be 1-3:2-5；PbO-H₃AsO₄·1/2H₂PbO and H in O system₃AsO₄· 1/2H₂The molar ratio of O is 1-3:2-5；ZnO-TeO₂ZnO and TeO in system₂Molar ratio be 1-5:2-5；ZnO-H₆TeO₆System Middle ZnO and H₆TeO₆Molar ratio be 1-6:2-5；ZnO-TeO₂-As₂O₅ZnO, TeO in system₂With As₂O₅Molar ratio is 1-5:2- 6:1-6；ZnO-H₆TeO₆-As₂O₅ZnO, H in system₆TeO₆With TeO₂Molar ratio is 1-5:2-5:2-6；ZnO-As₂O₅In system ZnO and As₂O₅Molar ratio is 1-3:3-6；ZnO-H₃AsO₄·1/2H₂ZnO and H in O system₃AsO₄·1/2H₂O molar ratio is 1- 3:3-6；PbO and ZnO molar ratio are 1-3:1-3 in PbO-ZnO system；PbO-ZnO-TeO₂PbO, ZnO and TeO in system₂Mole Than for 1-3:1-3:3-6；PbO-ZnO-H₆TeO₆PbO, ZnO and H in system₆TeO₆Molar ratio is 1-3:1-3:3-6；PbO- ZnO-As₂O₅PbO, ZnO and As in system₂O₅Molar ratio is 1-3:1-3:2-5；PbO-ZnO-H₃AsO₄·1/2H₂In O system PbO, ZnO and H₃AsO₄·1/2H₂O molar ratio is 1-3:1-3:3-6.

Arsenic acid tellurium zinc lead nonlinear optical crystal prepared by the present invention, it is characterised in that the chemical formula of the crystal is Pb₃Zn₃TeAs₂O₁₄, molecular weight 1319.2 do not have symmetrical centre, belongs to trigonal system, space group P321, cell parameter is Its powder SHG effect About 3 times of KDP (KH₂PO₄)。

Due to having used such as PbO, TeO during growing arsenic acid tellurium zinc lead nonlinear optical crystal₂、As₂O₅、 H₃AsO₄·1/2H₂O、PbF₂、H₆TeO₆、H₂TeO₃、Pb(NO₃)₂Deng from fluxing agent and such as PbO-TeO₂、PbO-H₆TeO₆、 PbO-TeO₂-As₂O₅、PbO-H₆TeO₆-H₃AsO₄·1/2H₂O、PbO-As₂O₅、PbO-H₃AsO₄·1/2H₂O、ZnO-TeO₂、 ZnO-H₆TeO₆、ZnO-TeO₂-As₂O₅、ZnO-H₆TeO₆-As₂O₅、ZnO-As₂O₅、ZnO-H₃AsO₄·1/2H₂O、PbO-ZnO、 PbO-ZnO-TeO₂、PbO-ZnO-H₆TeO₆、PbO-ZnO-As₂O₅、PbO-ZnO-H₃AsO₄·1/2H₂Other compound hydrotropies such as O Agent, product purity is high, and crystal is easily grown up and transparent no package, has the speed of growth very fast, at low cost, is easy to get larger size The advantages that crystal；Obtained crystal has than wider transmission region, and hardness is larger, good mechanical property, not easily broken and deliquescence, easily In the processing and preservation the advantages that.It is made of the compound arsenic acid tellurium zinc lead nonlinear optical crystal that the method for the invention obtains Device for non-linear optical make light source with Nd:YAG Q-switched laser at room temperature, incident wavelength is the infrared light of 1064nm, defeated Wavelength is the green laser of 532nm out, and laser intensity is equivalent to KDP (KH₂PO₄) 3 times.

Detailed description of the invention

Fig. 1 is Pb of the present invention₃Zn₃TeAs₂O₁₄The X-ray diffractogram of powder.

Fig. 2 is Pb of the present invention₃Zn₃TeAs₂O₁₄The working principle diagram of the device for non-linear optical of crystal production, wherein 1 is sharp Light device, 2 is issue light beam, and 3 be Pb₃Zn₃TeAs₂O₁₄Crystal, 4 be outgoing beam, and 5 be filter plate.

Specific embodiment

Below in conjunction with drawings and examples, the present invention is described in detail: