CN102304697B - Method for preparing diamond - Google Patents
Method for preparing diamond Download PDFInfo
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- CN102304697B CN102304697B CN 201110287391 CN201110287391A CN102304697B CN 102304697 B CN102304697 B CN 102304697B CN 201110287391 CN201110287391 CN 201110287391 CN 201110287391 A CN201110287391 A CN 201110287391A CN 102304697 B CN102304697 B CN 102304697B
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Abstract
The invention relates to the technical field of diamond preparation, in particular to a method for preparing diamond by using atomic layer deposition equipment. The method specifically comprises the following steps: putting a silicon substrate in a reaction chamber of the atomic layer deposition equipment; transporting a carbon-containing precursor to the reaction chamber of the atomic layer deposition equipment by way of carrier gas transport; and accumulating carbon atoms in the carbon-containing precursor on the silicon substrate through plasma discharge to spontaneously form a diamond structure. The method has the following beneficial effects that: the diamond can be prepared under a low-temperature and low-pressure condition by utilizing the atomic layer deposition equipment and common carbon sources; and the impurity content and structural integrity of the diamond can be controlled.
Description
Technical field
The present invention relates to the diamond preparing technical field, be specifically related to a kind ofly prepare adamantine method with atomic layer deposition apparatus.
Background technology
Diamond is commonly called as diamond, and it is a kind of allotropic substance of graphite, and it is one of the hardest material of occurring in nature.It has the characteristics such as superhard, wear-resisting, that thermal conduction is fast.In addition, diamond seems glittering and blazes because specific refractory power is high, becomes the jewel of Ms's favorite under light.On industrial production, diamond is mainly for the manufacture of drill bit and grinding tool.
The adamantine method of preparation mainly contains High Temperature High Pressure conversion method and PVD, the CVD method etc. of graphite at present.High temperature and high pressure method will expend more energy, the standby film quality of cutting is bad, the PVD method obtains diamond by the sputter graphite target, but the film that generally obtains is all the mixture of diamond and decolorizing carbon, and the benefit of the method is the dependence that can effectively reduce temperature.The CVD method makes starting material decompose by the methods such as burning, plasma body or heated filament activation starting material, and deposition prepares voluntarily; The method advantage is the dependency of temperature and pressure low, and the scope in source is wide, although the foreign matter content of the film that makes with respect to High Temperature High Pressure conversion method and PVD method is less, but still contains higher impurity level.
Summary of the invention
The object of the present invention is to provide a kind of adamantine preparation method, described method can be prepared has complete structure, functional strong diamond.
In order to achieve the above object, the technical solution used in the present invention is:
A kind of adamantine preparation method comprises the steps:
At surface of silicon evaporation or sputter layer of metal sodium;
Described silicon substrate is positioned in the atomic layer deposition apparatus reaction chamber;
To contain carbon matrix precursor by the carrier gas mode of transport is delivered in described atomic layer deposition apparatus reaction chamber;
By plasma discharge, make the carbon atom that contains in carbon matrix precursor accumulate on silicon substrate, spontaneous formation diamond lattic structure.
In such scheme, describedly also comprised before the step of surface of silicon evaporation layer of metal sodium: the surface of described silicon substrate is cleaned through reference liquid.
In such scheme, described carrier gas is hydrogen.
In such scheme, the flow of described carrier gas is 20sccm-100sccm.
In such scheme, the described carbon matrix precursor that contains is methane, ethene, acetylene, tetracol phenixin, carbon tetrabromide or methylene dichloride.
In such scheme, the described flow that contains carbon matrix precursor is 1sccm-10sccm.
In such scheme, described carrier gas and the described volume ratio that contains carbon matrix precursor are 40:1-20:1.
In such scheme, in described plasma discharge process, plasma power is 20W-150W.
Compare with the prior art scheme, the beneficial effect that the technical solution used in the present invention produces is as follows:
The present invention utilizes atomic layer deposition apparatus and common carbon source just can prepare diamond under low-temp low-pressure, and can control the integrity of adamantine foreign matter content and structure.
Description of drawings
Fig. 1 is the schematic diagram of the treated formation of surface of silicon Si-H key in the embodiment of the present invention;
Fig. 2 is the schematic diagram after surface of silicon evaporation or sputter one deck sodium metal in the embodiment of the present invention;
Fig. 3 passes into the schematic diagram of methylene dichloride to the ald reaction chamber in the embodiment of the present invention;
Fig. 4 is the schematic diagram that in the embodiment of the present invention, methylene dichloride and surface of silicon react;
Fig. 5 passes into the schematic diagram of hydrogen to the ald reaction chamber in the embodiment of the present invention;
Fig. 6 is the schematic diagram that in the embodiment of the present invention, the hydrogen atom after hydrogen gas ionizes replaces the chlorine atom of surface of silicon;
Fig. 7 is the schematic diagram that in the embodiment of the present invention, the hydrogen atom after hydrogen gas ionizes replaces the chlorine atom of surface of silicon fully.
Embodiment
Below in conjunction with drawings and Examples, technical solution of the present invention is described in detail.
The present embodiment provides a kind of adamantine preparation method, specifically comprises the steps:
Step 101 by the surface of reference liquid and hydrofluoric acid treatment silicon (111) substrate, forms si-h bond in surface of silicon, and as shown in Figure 1, wherein, reference liquid refers to: No. 1 liquid, the vitriol oil: hydrogen peroxide=4:1; No. 2 liquid, ammoniacal liquor: pure water: hydrogen peroxide=1:5:1; No. 3 liquid, hydrochloric acid: hydrogen peroxide: pure water=1:1:6;
Step 102 at surface of silicon evaporation or sputter layer of metal sodium, as shown in Figure 2, and is positioned over silicon substrate in the atomic layer deposition apparatus reaction chamber;
Step 103, opening device is adjusted working parameter, reaches the required Working environment of experiment; Take hydrogen as carrier gas, pass into methylene dichloride CH in the atomic layer deposition apparatus reaction chamber
2Cl
20.5s, as shown in Figure 3; Wherein the flow of hydrogen is 20sccm-100sccm, and the flow of methylene dichloride is 1sccm-10sccm, and the volume ratio of hydrogen and methylene dichloride is 40:1-20:1; Hydrogen serves as carrier gas and activator in this step;
Methylene dichloride and surface of silicon react, and as shown in Figure 4, reaction formula is:
Step 104 as shown in Figure 5, is carried out plasma discharge to carrier gas hydrogen in the atomic layer deposition apparatus reaction chamber, discharge power is controlled between 20W-150W, and preferably discharge power is 50W; Hydrogen atom after hydrogen gas ionizes replaces the chlorine atom of surface of silicon, as shown in Figure 6; After the chlorine atom of surface of silicon is replaced fully by hydrogen atom, as shown in Figure 7; Hydrogen in order to control the ratio of decomposing rear hydrocarbon atom, makes the carbon atom in methylene dichloride accumulate on silicon substrate, spontaneous formation diamond lattic structure on the one hand in order to control the split amount of precursor on the other hand;
Step 105 according to required thickness, repeats above step 103 and step 104, can successively bear the carbon membrane structure on substrate, because this carbon membrane structure of matching with silicon substrate is diamond lattic structure.
In the present embodiment, can also use the materials such as methane, ethene, acetylene, tetracol phenixin, carbon tetrabromide as containing carbon matrix precursor in step 103.
The present invention puts into suitable substrate in cavity, mode with the carrier gas transportation is transported to precursor in cavity, the strict flow of controlling carrier gas and precursor, pass through plasma discharge, make precursor ionization, the growth of film is controlled in the variation of the content by carrier gas and plasma power afterwards.Finally realize the accumulation of carbon, spontaneous formation has the diamond lattic structure of complete structure.
In sum, the present invention utilizes ALD equipment and common carbon source just can prepare diamond under low-temp low-pressure, and the variation that can utilize hydrogen content affects the formation of diamond lattic structure, and can be by the reductibility of hydrogen, the graphite-structure that decompose to generate, and affect the carrying out of reaction by the Sauerstoffatom that plasma body ionize the precursor generation.
The above is only the preferred embodiments of the present invention, is not limited to the present invention, and for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any modification of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (1)
1. an adamantine preparation method, is characterized in that, comprises the steps:
(1) by the surface of reference liquid and hydrofluoric acid treatment silicon substrate, form si-h bond in described surface of silicon; Wherein, reference liquid refers to: No. 1 liquid, the vitriol oil: hydrogen peroxide=4:1; No. 2 liquid, ammoniacal liquor: pure water: hydrogen peroxide=1:5:1; No. 3 liquid, hydrochloric acid: hydrogen peroxide: pure water=1:1:6;
(2) at surface of silicon evaporation or sputter layer of metal sodium;
(3) silicon substrate is positioned in the atomic layer deposition apparatus reaction chamber;
(4) take hydrogen as carrier gas, methylene dichloride is delivered in described atomic layer deposition apparatus reaction chamber; The flow of hydrogen is 20sccm-100sccm, and the flow of methylene dichloride is 1sccm-10sccm, and the volume ratio of hydrogen and methylene dichloride is 40:1-20:1; Methylene dichloride and surface of silicon react, and reaction formula is:
CH
2Cl
2+Na→CH
2Cl-CH
2Cl+NaCl；
(5) in the atomic layer deposition apparatus reaction chamber, hydrogen is carried out plasma discharge, discharge power is 50W; Hydrogen atom after hydrogen gas ionizes replaces the chlorine atom of surface of silicon, makes the carbon atom in methylene dichloride accumulate on silicon substrate, spontaneous formation diamond lattic structure.
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| CN 201110287391 CN102304697B (en) | 2011-09-26 | 2011-09-26 | Method for preparing diamond |
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| CN 201110287391 CN102304697B (en) | 2011-09-26 | 2011-09-26 | Method for preparing diamond |
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| CN102304697B true CN102304697B (en) | 2013-06-12 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101680087A (en) * | 2007-03-06 | 2010-03-24 | 瓦里安半导体设备公司 | Technique for atomic layer deposition |
| CN101775592A (en) * | 2009-01-09 | 2010-07-14 | 信越化学工业株式会社 | Direct-current plasma CVD apparatus and method for producing diamond using the same |
| CN101981659A (en) * | 2008-03-05 | 2011-02-23 | 应用材料股份有限公司 | Method for depositing an amorphous carbon film with improved density and step coverage |
| CN102304696A (en) * | 2011-09-23 | 2012-01-04 | 中国科学院微电子研究所 | Method for preparing diamond |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0764675B2 (en) * | 1986-05-27 | 1995-07-12 | 洋一 広瀬 | Diamond synthesis method |
| US7959985B2 (en) * | 2006-03-20 | 2011-06-14 | Tokyo Electron Limited | Method of integrating PEALD Ta-containing films into Cu metallization |
| US10378106B2 (en) * | 2008-11-14 | 2019-08-13 | Asm Ip Holding B.V. | Method of forming insulation film by modified PEALD |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101680087A (en) * | 2007-03-06 | 2010-03-24 | 瓦里安半导体设备公司 | Technique for atomic layer deposition |
| CN101981659A (en) * | 2008-03-05 | 2011-02-23 | 应用材料股份有限公司 | Method for depositing an amorphous carbon film with improved density and step coverage |
| CN101775592A (en) * | 2009-01-09 | 2010-07-14 | 信越化学工业株式会社 | Direct-current plasma CVD apparatus and method for producing diamond using the same |
| CN102304696A (en) * | 2011-09-23 | 2012-01-04 | 中国科学院微电子研究所 | Method for preparing diamond |
Non-Patent Citations (2)
| Title |
|---|
| 毕京锋等.等离子体辅助热丝化学气相沉积金刚石膜.《青岛科技大学学报》.2004,第25卷(第1期),第36～38页. |
| 等离子体辅助热丝化学气相沉积金刚石膜;毕京锋等;《青岛科技大学学报》;20040229;第25卷(第1期);第36～38页 * |
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