CN1782123A - Diamond-like carbon film and its preparing method - Google Patents
Diamond-like carbon film and its preparing method Download PDFInfo
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- CN1782123A CN1782123A CN 200410096585 CN200410096585A CN1782123A CN 1782123 A CN1782123 A CN 1782123A CN 200410096585 CN200410096585 CN 200410096585 CN 200410096585 A CN200410096585 A CN 200410096585A CN 1782123 A CN1782123 A CN 1782123A
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Abstract
The present invention provides a kind of diamond-like carbon film with less wear loss, capacity of being low temperature formed and high adhesion and its preparation process. During the preparation, one intermediate layer containing organic Si-O compound is first formed on one substrate via film deposition with organic Si-O compound, such as hexamethyl disiloxane, and hydrogen and carbon source in gradually changed ratio; and one diamond-like carbon layer is then deposited on the intermediate layer with the hydrogen and carbon source, so as to form one diamond-like carbon film with high adhesion. The diamond-like carbon film has proper hardness/toughness ratio, and the intermediate layer possesses sufficient mechanical support, so that the high hardness diamond-like carbon film is attached to the substrate firmly.
Description
Technical field
(Diamond-Like Carbon, DLC) film and preparation method thereof particularly a kind ofly are plated on diamond-like carbon film on the base material and forming process thereof with the plasma foil sedimentation to the present invention relates to a kind of diamond-like carbon of high adhesive force.
Background technology
Diamond-like carbon (DLC) film has characteristics such as high rigidity, erosion resistance, surface smoothing, frictional coefficient are little, the close system height of film, electrical insulating property is good, heat conductivity is good, bio-compatibility is good, can grow up at low temperatures.Therefore diamond-like carbon film can be applied in mould, cutting tool, optical module, electronic package, external coating and give birth among doctor's material.
Generally speaking, the generation of diamond-like carbon film is to produce hydrocarbon polymer ion (CH in plasma body
x +) quicken and penetrate the film that substrate surface forms high rigidity, wear-resistant and dark tool industrial application value.Yet, there is a stress under compression among this film, this stress can influence the diamond-like carbon material to the base material adhesive ability.
For head it off, industrial generally is to increase by a middle layer between base material and diamond-like carbon film, for example titanium nitride, titanium carbide, (multilayer coating) utilizes the plated film mode of multilayer film to form a multilayer film middle layer, with as difference row (dislocation) mobile barrier layer,, utilization rete interface generate energy deviation improves the surface attachment degree but discharging the characteristic of residual stress.Yet this way need suitably be controlled the hardness/tough sex ratio of multilayer film combination, and too the high adhesive force deficiency is not shock-resistant as if hardness; Though if the too high impact resistance of toughness is good, hardness has problem such as do not resistance to wear inadequately again.Moreover titanium nitride and titanium carbide belong to high-temperature technology (service temperature is about 450 ℃), and plating diamond-like carbon material is a low temperature process, must wait for after the temperature decline in middle layer, just can plate the diamond-like carbon material at last; Between temperature one rise and one drop, not only cause the waste of the time and the energy, the thermal stresses of the diamond-like carbon film sticking power that also exerts an influence.
Add titanium nitride, titanium carbide in acidity or alkaline environment than the unprotect ability, therefore having need provide a kind of and have high adhesive ability, abrasion performance, can be formed by low temperature process, and the good diamond-like carbon film of mesospheric chemistry inertia.
Summary of the invention
Main purpose of the present invention provides an abrasion performance, can be formed by low temperature process, and has the high adhesive force diamond-like carbon film in the good middle layer of a unreactiveness.
According to the present invention, mainly be to utilize the organosilicon oxygen compound, hexamethyldisiloxane (Hexamethyldisiloxane for example, HMDSO) mix hydrogeneous carbon source, with the method for thin film deposition, continuously change the ratio of organosilicon oxygen compound, on base material, form a progressive middle layer.This middle layer is to be scattered among the diamond-like carbon material with the molecular level state by silica functional group (Si-O-Si), and the density of silica functional group changes gradually along the thickness in middle layer.At last above the middle layer, do the top layer that thin film deposition plating essence is the diamond-like carbon material, to form the diamond-like carbon film of high adhesive force with hydrogeneous carbon source.
The present invention at first provides a kind of diamond-like carbon film, comprises at least:
One base material;
One middle layer is positioned on the described base material, and this middle layer has the Si oxide material at least; And
One top layer is positioned at top, described middle layer.
Wherein said middle layer can comprise a single layer structure, a multilayered structure or one progressive layer of structure.This middle layer is sneaked into the silica material and is formed in the diamond-like carbon material, this silica material comprises silicon oxide or contains the material of silica functional group.The distribution density of described silica functional group is along with the thickness position in silica middle layer gradually changes.
Simultaneously, the present invention also provides a kind of manufacture method of diamond-like carbon film, comprises at least:
One base material is provided;
Form a middle layer on described base material, this middle layer has the silica material at least; And
Form a top layer in this top, middle layer.
The method in wherein said formation middle layer also comprises: form a diamond-like carbon material in described substrate, and sneak into the silica material in the diamond-like carbon material; Perhaps, form a silica material in described substrate, and sneak into the diamond-like carbon material in this silica material.
According to specific embodiments of the present invention, the method in described formation middle layer also can comprise:
Mix feeding one organosilicone compounds and a hydrogeneous carbon source to carry out a depositing operation;
Change the ratio of described organosilicon oxygen compound and hydrogeneous carbon source gradually.
Among the present invention, optional in the group that methane, ethane, acetylene, ethene, benzene are formed one or more of described hydrogeneous carbon source.
In diamond-like carbon film technology, the invention provides the middle layer of a low temperature process.Because the technological temperature on diamond-like carbon material top layer is lower than the high-temperature technology of conventional art, therefore low temperature process of the present invention middle layer cooling waiting time and the heat energy of not only having saved plating diamond-like carbon material top layer expends, and provide appropriate hardness/tough sex ratio, make the middle layer have enough mechanical support power, more make the diamond-like carbon material top layer of high rigidity be attached to difficult drop-off on the base material.Hardness test confirms that under proper condition critical load is greater than more than 50 newton, and hardness can reach 21.75 * 109 handkerchiefs (Pa).
The present invention also makes Thermal Stress Experiment at the high adhesive force diamond-like carbon film, with stability test.The sticking power and the hardness that show diamond-like carbon film of the present invention are not influenced by thermal stresses.Temperature up to 400 ℃ environment under structure can not change to some extent yet.
Can confirm that by above-described test-results diamond-like carbon film provided by the present invention has sticking power height, abrasion performance, can form by low temperature process, and the good technical superiority of mesospheric chemistry inert.
Description of drawings
Fig. 1 is the operating system synoptic diagram that illustrates the plasma ion evaporation process.
Fig. 2 illustrates the progressive layer decomposing schematic representation of formed diamond-like carbon film on the steel base material according to a preferred embodiment of the invention.
Fig. 3 is the Raman spectrum analysis figure according to stability test of the present invention illustrated.
Conventional letter simple declaration among the figure:
10 base materials, 20 silica middle layers, 30 quasi-diamond carbon-coatings
Embodiment
According to a preferred embodiment of the invention, the diamond-like carbon film of high adhesive force comprises the top layer that the middle layer that is formed at the oxide containing silicon on metal or the non-metal solid base material and essence are the diamond-like carbon material.
Described middle layer has silica (Si-O-Si) functional group.Silica functional group be a kind of be the warp architecture at center with oxygen, this warp architecture helps the absorption of stress of diamond-like carbon film itself, to strengthen the adhesive ability on diamond-like carbon material top layer.In certain embodiments, base materials such as diamond-like carbon material top layer and steel, wolfram steel, nickel, chromium, aluminium are combined closely.According to some embodiments of the present invention, the middle layer can be a single layer structure, a multilayered structure or one progressive layer of structure, but is preferably one progressive layer of structure.
The formation in middle layer, at first organosilicone compounds being mixed hydrogeneous carbon source feeds in the reactor, do not have a progressive layer of violent change through the character of thin film deposition processes between form layers on the base material and layer, in the middle of technology, change the ratio of organosilicon oxygen compound gradually, with the distribution density of control silica functional group (Si-O-Si).
In a preferred embodiment of the invention, organosilicone compounds, for example (Hexamethyldisiloxane, unit chemical formula HMDSO) is (CH to hexamethyldisiloxane
3)
3SiOSi (CH
3)
3, and hydrogeneous carbon source is a methane.Employed thin film deposition processes comprises chemical vapour deposition, ion evaporation or sputter, is preferably the plasma ion evaporation process.Fig. 1 illustrates the employed operating system of plasma ion evaporation process.In this preferred embodiment, substrate carrier is passed to the high frequency power supply, vacuum chamber body wall generation capacitor discharge with reactor dissociates working gas (HMDSO and methane) again, and its ion is obtaining energy and directly bombarding substrate by self-bias voltage high-frequency (self bias).Operation pressure maintains 1.9 * 10
-2Bristol (torr), high frequency power are 100W.The plasma ion evaporation process of working gas (HMDSO and methane) belongs to low temperature process, and service temperature is less than 300 ℃.
In this preferred embodiment, the proportional range of organosilicone compounds (HMDSO) and methane gradually changes along deposit thickness between 32% to 0.1%.Fig. 2 illustrates according to a preferred embodiment of the invention, the progressive layer of formed diamond-like carbon film decomposing schematic representation on steel substrate, the ratio distribution scenario of demonstration organosilicone compounds (HMDSO) and methane.In this preferred embodiment, organosilicone compounds (HMDSO) the ratio gradient that is positioned on the steel substrate 10 upwards is decremented to 0.1% in regular turn by the highest 32% thickness along silica middle layer 20, and the intermediate layer thickness scope is between 1.2 μ m to 3 μ m.In another embodiment of the present invention, the method that forms this middle layer more comprises, for example forms a diamond-like carbon material earlier in substrate, the silica material is mixed in the diamond-like carbon material again.In another embodiment of the present invention, the method that forms this middle layer more comprises, for example forms a silica material earlier in substrate, the diamond-like carbon material is mixed in this silica material again.
Form a quasi-diamond carbon-coating 30 in the top, middle layer at last, to form the diamond-like carbon film of a high adhesive force.This diamond-like carbon layer 30 is made up of the diamond-like carbon material; Wherein the formation of quasi-diamond carbon-coating 30 is 100% hydrogeneous carbon source to be fed in the reactor form through thin film deposition processes.In this preferred embodiment, hydrogeneous carbon source is a methane, and employed thin film deposition processes comprises chemical vapour deposition, ion evaporation or sputter, is preferably the plasma ion evaporation process.This thin film deposition processes is that substrate carrier is passed to the high frequency power supply equally, make the vacuum chamber body wall of reactor produce electric capacity and put plasma methane and dissociate, make the methane ion directly bombard substrate by the resulting energy of self-bias voltage high-frequency (self bias).Operation pressure maintains 1.9 * 10
-2Bristol (torr), high frequency power are 100W.Preferred diamond-like carbon layer thickness scope is 0.1 μ m to 0.5 μ m.
For proving that diamond-like carbon film provided by the present invention has the characteristic of high adhesive force, high rigidity, abrasion performance, the diamond-like carbon film that the present invention is directed to high adhesive force is made Thermal Stress Experiment, with stability test.
Thermal Stress Experiment is that diamond-like carbon film provided by the present invention is placed in the baking oven, and temperature is controlled at normal temperature and 400 ℃ respectively and kept recirculation 50 times respectively 20 minutes; Carry out microhardness again and measure and draw together the trace test.Under opticmicroscope, observe the scratch test result, when the diamond head heavy burden reaches 50 Newtonian times, what diamond-like carbon film was still good is attached on the substrate, observe the hardness measurement result down in atomic force microscope (AFM) and find that also hardness value does not descend, show that diamond-like carbon film of the present invention is not influenced by thermal stresses.
Stability test is this bright diamond-like carbon film that provides to be placed under the environment of 400 ℃ of temperature kept 2 hours, carries out Raman (Raman) spectroscopic analysis again.Fig. 3 is according to the Raman spectrum analysis figure that stability test of the present invention illustrated, and two absorption spectrums among the figure before and after the test have the extinction crest to occur in wave number 1500 and 3750 respectively, and expression spectrographic extinction wavelength does not change; The structure that shows the diamond-like carbon film of high adhesive force does not change (structure greying) to some extent under this environment.
Though traditional kinds of interlayer, the temperature that titanium nitride, titanium carbide can Nai Genggao for example, but the middle layer of diamond-like carbon film provided by the present invention is made of silicon oxide compound and diamond-like carbon material, has preferable unreactiveness in acidity or alkaline environment.
Can confirm that according to above explanation diamond-like carbon film provided by the present invention has sticking power height, hardness height, abrasion performance really, can be formed by low temperature process, and the good technical superiority of mesospheric chemistry inert.
Though above-described embodiment has described technical characterictic of the present invention and advantage in detail, yet it should be noted that, any retouching that surpasses the present invention's spirit scope still is contained in protection scope of the present invention with change, for example, diamond-like carbon film structure of the present invention can for, at least the multilayered structure that has a middle layer and a top layer is not limited to the disclosed scope of the above embodiment; Above-described embodiment is only in order to set forth content of the present invention but not in order to limit the scope of the invention, protection scope of the present invention should be as the criterion with claim.
Claims (14)
1. diamond-like carbon film comprises at least:
One base material;
One middle layer is positioned on the described base material, and this middle layer has the Si oxide material at least; And
One top layer is positioned at top, described middle layer.
2. diamond-like carbon film as claimed in claim 1, wherein said middle layer comprise a single layer structure, a multilayered structure or one progressive layer of structure.
3. diamond-like carbon film as claimed in claim 2, wherein said top layer also further comprise a diamond-like carbon material.
4. diamond-like carbon film as claimed in claim 3, wherein said middle layer are sneaked into the silica material and are formed in the diamond-like carbon material.
5. diamond-like carbon film as claimed in claim 4, wherein said silica material comprise silicon oxide or contain the material of silica functional group.
6. diamond-like carbon film as claimed in claim 5, the distribution density of wherein said silica functional group is along with the thickness position in silica middle layer gradually changes.
7. the manufacture method of a diamond-like carbon film comprises at least:
One base material is provided;
Form a middle layer on described base material, this middle layer has the silica material at least; And
Form a top layer in this top, middle layer.
8. the manufacture method of diamond-like carbon film as claimed in claim 7, the method in wherein said formation middle layer also comprises:
Form a diamond-like carbon material in described substrate; And
Sneak into the silica material in the diamond-like carbon material.
9. the manufacture method of diamond-like carbon film as claimed in claim 7, the method in wherein said formation middle layer also comprises:
Form a silica material in described substrate; And
Sneak into the diamond-like carbon material in this silica material.
10. the manufacture method of diamond-like carbon film as claimed in claim 7, the method in wherein said formation middle layer also comprises:
Mix feeding one organosilicone compounds and a hydrogeneous carbon source to carry out a depositing operation;
Change the ratio of described organosilicon oxygen compound and hydrogeneous carbon source gradually.
11. the manufacture method of diamond-like carbon film as claimed in claim 10, wherein said organosilicone compounds comprise that the unit chemical formula is (CH
3)
3SiOSi (CH
3)
3Compound.
12. the manufacture method of diamond-like carbon film as claimed in claim 7, the formation method on wherein said top layer comprises:
Feed a hydrogeneous carbon source;
Carry out a thin film deposition processes.
13. the manufacture method of diamond-like carbon film as claimed in claim 12, the service temperature of wherein said thin film deposition processes is less than 300 ℃.
14. as the manufacture method of claim 10 or 13 described diamond-like carbon films, wherein said hydrogeneous carbon source is selected from one or more in methane, ethane, acetylene, ethene or the benzene.
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|---|---|---|---|
| CN 200410096585 CN1782123A (en) | 2004-12-03 | 2004-12-03 | Diamond-like carbon film and its preparing method |
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|---|---|---|---|
| CN 200410096585 CN1782123A (en) | 2004-12-03 | 2004-12-03 | Diamond-like carbon film and its preparing method |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101089221B (en) * | 2006-06-14 | 2010-05-12 | 中国砂轮企业股份有限公司 | Manufacturing method of diamond coating film and its application |
| CN102234785A (en) * | 2010-04-30 | 2011-11-09 | 永恒科技有限公司 | Substrate coating and forming method thereof |
| CN102453859A (en) * | 2010-10-29 | 2012-05-16 | 中国科学院兰州化学物理研究所 | Method for preparing hydrogen-containing DLC (diamond-like carbon film) material |
| CN102560413A (en) * | 2010-12-13 | 2012-07-11 | 财团法人金属工业研究发展中心 | Diamond-like carbon film and manufacturing method thereof |
| CN102808163A (en) * | 2011-05-30 | 2012-12-05 | 株式会社电装 | Sliding device and sliding system using the same |
| CN103374697A (en) * | 2012-04-20 | 2013-10-30 | 深圳富泰宏精密工业有限公司 | Surface treatment method and product of diamond-like carbon film layer |
| US8852746B2 (en) | 2010-04-30 | 2014-10-07 | Winsky Technology Limited | Substrate coating and method of forming the same |
| CN105648417A (en) * | 2016-03-14 | 2016-06-08 | 三峡大学 | Method for utilizing low-temperature chemical vapor deposition technology to prepare amorphous carbon film |
| US9605340B2 (en) | 2012-07-05 | 2017-03-28 | Intevac, Inc. | Method to produce highly transparent hydrogenated carbon protective coating for transparent substrates |
| CN108474871A (en) * | 2016-01-18 | 2018-08-31 | 住友电气工业株式会社 | Optical element |
| CN114447354A (en) * | 2022-01-26 | 2022-05-06 | 纳狮新材料有限公司 | Diamond-like carbon composite coating for metal polar plate and preparation method thereof |
-
2004
- 2004-12-03 CN CN 200410096585 patent/CN1782123A/en active Pending
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101089221B (en) * | 2006-06-14 | 2010-05-12 | 中国砂轮企业股份有限公司 | Manufacturing method of diamond coating film and its application |
| US8852746B2 (en) | 2010-04-30 | 2014-10-07 | Winsky Technology Limited | Substrate coating and method of forming the same |
| CN102234785A (en) * | 2010-04-30 | 2011-11-09 | 永恒科技有限公司 | Substrate coating and forming method thereof |
| CN102234785B (en) * | 2010-04-30 | 2013-08-21 | 永恒科技有限公司 | Substrate coating and forming method thereof |
| CN102453859A (en) * | 2010-10-29 | 2012-05-16 | 中国科学院兰州化学物理研究所 | Method for preparing hydrogen-containing DLC (diamond-like carbon film) material |
| CN102560413A (en) * | 2010-12-13 | 2012-07-11 | 财团法人金属工业研究发展中心 | Diamond-like carbon film and manufacturing method thereof |
| CN102560413B (en) * | 2010-12-13 | 2014-06-04 | 财团法人金属工业研究发展中心 | Diamond-like carbon film and manufacturing method thereof |
| CN102808163A (en) * | 2011-05-30 | 2012-12-05 | 株式会社电装 | Sliding device and sliding system using the same |
| CN103374697A (en) * | 2012-04-20 | 2013-10-30 | 深圳富泰宏精密工业有限公司 | Surface treatment method and product of diamond-like carbon film layer |
| US9605340B2 (en) | 2012-07-05 | 2017-03-28 | Intevac, Inc. | Method to produce highly transparent hydrogenated carbon protective coating for transparent substrates |
| CN108474871A (en) * | 2016-01-18 | 2018-08-31 | 住友电气工业株式会社 | Optical element |
| CN105648417A (en) * | 2016-03-14 | 2016-06-08 | 三峡大学 | Method for utilizing low-temperature chemical vapor deposition technology to prepare amorphous carbon film |
| CN114447354A (en) * | 2022-01-26 | 2022-05-06 | 纳狮新材料有限公司 | Diamond-like carbon composite coating for metal polar plate and preparation method thereof |
| CN114447354B (en) * | 2022-01-26 | 2022-11-25 | 纳狮新材料有限公司 | Diamond-like carbon composite coating for metal polar plate and preparation method thereof |
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