CN102650037A - Method for manufacturing magnetron sputtering target material of Mn-Co-Ni-O thin film - Google Patents
Method for manufacturing magnetron sputtering target material of Mn-Co-Ni-O thin film Download PDFInfo
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- CN102650037A CN102650037A CN2012101412245A CN201210141224A CN102650037A CN 102650037 A CN102650037 A CN 102650037A CN 2012101412245 A CN2012101412245 A CN 2012101412245A CN 201210141224 A CN201210141224 A CN 201210141224A CN 102650037 A CN102650037 A CN 102650037A
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Abstract
The invention discloses a method for manufacturing a magnetron sputtering target material of a Mn-Co-Ni-O thin film. The method mainly comprises the following steps of: 1, weighing acetate powder of manganese (Mn), acetate powder of cobalt (Co) and acetate powder of nickel (Ni); 2, dissolving the powders by using an aqueous solution of acetic acid to prepare a precursor solution; 3, performing negative-pressure suction filtration on the precursor solution to remove few contamination precipitations from the precursor solution by filtration, and putting the solution in an evaporation pan and drying to obtain dried acetate clots; 4, crushing the acetate clots, and performing baking, grinding, roasting and ball milling by using a high temperature oven to obtain manganese oxide powder of which the grain size is smaller and does not contain residual organic matter; 5, fetching a right amount of manganese oxide powder, adding a polyvinyl alcohol solution to the manganese oxide powder and pelleting and putting in a mould and pressing into a plain blank; 6, degumming stage by stage to remove polyvinyl alcohol from the plain blank; and 7, performing high-temperature sintering, cutting, grinding and polishing to obtain the required sputtering target material.
Description
Technical field
The present invention is applicable to a kind of making method of magnetic control spattering target of thermosensitive film, in particular, be involved in a kind of spinel structure the Mn-Co-Ni-O thermosensitive film the making method of magnetic control spattering target.
Background technology
The Mn-Co-Ni-O series material is a kind of thermo-sensitive material with very high negative temperature coefficient of resistance.Such oxide semiconductor material is because of its stable performance, and characteristics that working temperature is wide and obtained very big development are widely used in thermometric, temperature control, compensation, voltage stabilizing, remote control, flow, velocity measurement and the time lag equipment [1].In addition, this kind material has excellent specific properties such as broad spectral response and performance long-term stability, the low temperature temperature-sensitive of space technology survey and civilian uncooled ir detection aspect ten minutes important application [2,3] is arranged.Mn
1.56Co
0.96Ni
0.48O
4(being called for short MCN down) then has the resistivity of the minimum of this type of series material, therefore in the Mn-Co-Ni-O thermo-sensitive material, occupies critical role.Use chemical solution methods such as the Hou Yun of Shanghai technology physics institute have successfully prepared high-quality MCN polycrystal film on hot-pressure oxidation aluminium substrate; Make the miniaturized and the integrated possibility that becomes of this type of thermistor detector spare, greatly expanded the application prospect [4] of this material.
Along with the development of film preparing technology, multivariant oxide growth for Thin Film compound method is various day by day, chooses suitable material preparation method and can obtain big area, the uniform functional materials film of thickness.The method of Mn-Co-Ni-O series component negative temperature coefficient semiconductor material mainly contains methods such as high-temperature solid sintering process, sol-gel method, pulsed laser deposition and magnetron sputtering method.Mn-Co-Ni-O body material is generally made [5,6] with solid-state sintering, is about to oxide powder (manganese oxide, powder blue and nickel oxide) and mixes according to a certain percentage, and at high temperature sintering makes.The fault in material that this method makes is more, and is fine and close inadequately, thereby stability is relatively poor.The advantage of Prepared by Sol Gel Method Mn-Co-Ni-O thin-film material is that equipment is simple, cost is low, stoichiometric ratio is easy to control; Shortcoming is that quality of materials receives the influence of preparation process condition and external environment situation bigger, has very big empirically, and preparation parameter is difficult to quantize, and preparation cycle is long.Pulsed laser deposition utilizes high-energy focusing laser pulse bundle irradiation target material surface; The thin layer of target material surface is burnt, form twilight sunset, on substrate, gather film forming; The ratio of component of the film that its advantage is to prepare and the stoichiometric ratio of target are consistent; Shortcoming is that the normal cohesion in film surface forms subparticle and makes surface quality undesirable, is unfavorable for preparing large area film [7].And utilize magnetically controlled sputter method to prepare film, have then that thin film composition is fine and close evenly, film forming speed is fast, a stable performance, film adhesion strength advantages of higher.The Ni that external existing bibliographical information utilizes magnetron sputtering method to make
1-xCo
xO
4/3(0<x<1) series thin film, the specific conductivity of being reported for work are compared better, the specific conductivity higher [8] of density of the film of Prepared by Sol Gel Method.
Because the Mn-Co-Ni-O film is less at the uptake factor of infrared (2 μ m-15 μ m); Therefore; The Mn-Co-Ni-O film that need prepare thicker (8-10 μ m is thick); And mating surface coats the absorptive thermal radiation that the method for platinum black or organism absorption layer could be as much as possible, realizes very broadband infrared acquisition [9].Satisfied the requirement of the sensitive detection parts preparation of short run with the Mn-Co-Ni-O thin-film material of sol-gel method growth, but its efficient is lower, the long and quality of forming film of preparation cycle receives the influence of environment easily.Therefore; Angle from the magnetron sputtering sputtering method; Developing the method for a kind of quick preparation than the serial component film of big area Mn-Co-Ni-O, improve the preparation efficiency and the quality of forming film of the thermosensitive material film of MCN and part usual component, is a kind of work of very promising and researching value.Utilize this method, be hopeful comparatively fast to prepare applicable to the interval high-quality Mn-Co-Ni-O thermosensitive film of differing temps.At present, the method for magnetron sputtering prepare MCN material aspect rarely have the report or patent documentation can be for reference.This patent will provide the preparation method of the magnetron sputtering of Mn-Co-Ni-O thermosensitive film with target.
More than related reference following:
1. king zero is gloomy etc., special cermacis. press of Zhongnan Polytechnic Univ, 1994:p.330-338.
2.Kanade,S.A.and?V.Puri,Composition?dependent?resistivity?NTC?of?thick?film?Ni
(1-x)Co
xMn
2O
4:(0≤x≤1)NTC?thermistors.Materials?Letters,2006.60(11):p.1428-1431.
3.Tissot,J.L.,IR detection?with?uncooled sensors.Infrared?Physics?&Technology,2004.46(1-2):p.147-153.
4.Hou,Y.,et?al.,Characterization?of?Mn
(1.56)Co
(0.96)Ni
(0.48)O
(4)films?for?infrared?detection.Applied?Physics?Letters,2008.92(20).
5.Park,K.,et?al.,Improvement?in?the?electrical?stability?of?Mn-Ni-Co-ONTC?thermistors?by?substituting?Cr
2O
3?for?Co
3O
4.Journal?of?Alloys?and?Compounds,2007.437(1-2):p.211-214.
6.Basu,A.,et?al.,In?situ?study?of?the?effect?of?temperature?on?the?electronic?structure?of?NixMn3-xO4+delta?thin?films?using?scanning?tunneling?spectroscopy.Journal?of?Applied?Physics,2002.92(7):p.4123-4125.
7.Kim,D.W.,et?al.,Structural?and?optical?properties?of?LiNbO
3?films?grown?by?pulsed?laser?deposition?with?a?shadow?mask.Japanese?Journal?of?Applied?Physics?Part?1-Regular?Papers?Short?Notes&Review?Papers,1998.37(4A):p.2016-2020.
8.Windisch,C.F.,et?al.,Conducting?spinel?oxide?films?with?infrared?transparency.Thin?Solid?Films,2002.420:p.89-99.
9. the 3rd research department's temperature-sensitive device group, the thermosensitive resistance infrared detector development report. infrared and millimeter wave journal, 1975. the third phase.
Summary of the invention:
The sputtering target material preparation method who the purpose of this invention is to provide a kind of manganese cobalt nickel oxygen material provides a kind of technique means for solving the problem that follow-up magnetron sputtering method prepares the required target of Mn-Co-Ni-O thermosensitive film.
The objective of the invention is to realize like this:
1. the acetate powder of weighing manganese, cobalt, nickel.For target components is (Mn
xNi
1-x) (Mn
yCo
1-y)
2O
4Mn oxide, in four water acetic acid manganese: Cobalt diacetate tetrahydrate: the mass ratio of four water acetic acid nickel is (245.09 (x+2y)): (249.08 (2-2y)): the ratio of (248.71 (1-x)) takes by weighing acetate.
2. prepare precursor solution.Use the aqueous solution of acetic acid that powder is dissolved, the ratio that adds 200ml acetic acid, 400ml water according to every 100g acetate is prepared precursor solution.
3. filter out impurities oven dry.Precursor solution is poured in the solution splendid attire ware of negative pressure leaching machine, selecting the aperture for use is the filter membrane of 0.45 μ m, carries out negative pressure leaching, filtering small amount of impurities deposition wherein.Solution is made in the furnace pot of packing into, and oven dry obtains exsiccant acetate grumeleuse.
4. preparation oxide powder.The acetate grumeleuse is smashed to pieces, used high temperature oven to burn, remove remaining moisture and most organism, obtain black gray Mn oxide powder 400 ℃ of bakings of carrying out 4 hours.In agate mortar, ground about 20 minutes, the range estimation diameter of particle is no more than 1mm, continue to use high temperature oven 850 ℃ down baking burnt 6 hours, obtain particle diameter less, do not have a remaining organic manganese oxide powder.
5. make plain embryo.Ball milling 8 hours obtains median size less than 1 micron manganese oxide powder.The polyvinyl alcohol solution that adds mass ratio 5%-8%, granulation.Put into mould,, obtain plain embryo the static pressure pressed of 40-60Mpa 40 minutes.
6. segmentation is come unstuck.Use high temperature oven to carry out segmentation and come unstuck, 100 ℃ one hour, 200 ℃ one hour, 300 ℃ one hour, 400 ℃ one hour, 500 ℃ two hours, remove the Z 150PH in the plain embryo.
7. high temperature sintering.Segmentation is warmed up to 1050 ℃-1200 ℃ after coming unstuck and accomplishing in High Temperature Furnaces Heating Apparatus, be incubated 8 hours.Naturally take out cooling back, cutting obtain desired size ceramic target.Polishing, polishing.
Description of drawings:
Fig. 1 is the method flow of target preparation.
Fig. 2 is the X-ray diffractogram of two kinds of targets, (a) is the diffractogram of manganese cobalt nickel oxygen, (b) is the diffractogram of nickel acid manganese.Both diffractograms all meet spinel structure.
Embodiment
Examples of implementation 1
Manganese cobalt nickel oxygen (Mn
1.56Co
0.96Ni
0.48O
4) preparation of thin-film material magnetic control spattering target
1. the acetate powder of weighing manganese, cobalt, nickel.For target components is Mn
1.56Co
0.96Ni
0.48O
4Mn oxide, take by weighing four water acetic acid manganese 91.76g respectively, Cobalt diacetate tetrahydrate 57.39g, four water acetic acid nickel 28.66g.
2. prepare precursor solution.Use the aqueous solution of acetic acid that powder is dissolved, the ratio that adds 200ml acetic acid, 400ml water according to every 100g acetate is prepared precursor solution.
3. filter out impurities oven dry.Precursor solution is poured in the solution splendid attire ware of negative pressure leaching machine, selecting the aperture for use is the filter membrane of 0.45 μ m, carries out negative pressure leaching, filtering small amount of impurities deposition wherein.Solution is made in the furnace pot of packing into, and oven dry obtains exsiccant acetate grumeleuse.
4. preparation oxide powder.The acetate grumeleuse is smashed to pieces, used high temperature oven to burn, remove remaining moisture and most organism, obtain manganese cobalt nickel oxygen powder 400 ℃ of bakings of carrying out 4 hours.Ground about 20 minutes, the range estimation diameter of particle is no more than 1mm, continue to use high temperature oven 850 ℃ down baking burnt 6 hours, obtain particle diameter less, do not have a remaining organic manganese oxide powder.
5. make plain embryo.Ball milling 8 hours obtains median size less than 1 micron manganese oxide powder.Take by weighing the 60g powder, add the polyvinyl alcohol solution of mass ratio 5%-8%, granulation.Put into mould, the static pressure pressed of 40-60Mpa 40 minutes, obtaining diameter was 78mm, and thickness is about the plain embryo of 4mm.
6. segmentation is come unstuck.Use high temperature oven to carry out segmentation and come unstuck, 100 ℃ one hour, 200 ℃ one hour, 300 ℃ one hour, 400 ℃ one hour, 500 ℃ two hours, remove the Z 150PH in the plain embryo.
7. high temperature sintering.After segmentation is come unstuck, in High Temperature Furnaces Heating Apparatus, be warmed up to 1050 ℃, be incubated 8 hours.Naturally cooling is taken out, and obtaining the target diameter is 66.22mm, and pyrocondensation is than being (78-66.22) mm/78=15.1%.Density is about 3.4gcm
-3, it is 61 millimeters ceramic target that cutting obtains diameter.Use sand papering, polishing.
Examples of implementation 2
Nickel acid manganese (NiMn
2O
4) preparation of thin-film material magnetic control spattering target
1. the acetate powder of weighing manganese, cobalt, nickel.For target components is NiMn
2O
4Mn oxide, take by weighing four water acetic acid manganese 117.65g respectively, four water acetic acid nickel 59.70g mix.
2. prepare precursor solution.Use the aqueous solution of acetic acid that powder is dissolved, the ratio that adds 200ml acetic acid, 400ml water according to every 100g acetate is prepared precursor solution.
3. filter out impurities oven dry.Precursor solution is poured in the solution splendid attire ware of negative pressure leaching machine, selecting the aperture for use is the filter membrane of 0.45 μ m, carries out negative pressure leaching, filtering small amount of impurities deposition wherein.Solution is made in the furnace pot of packing into, and oven dry obtains exsiccant acetate grumeleuse.
4. preparation oxide powder.The acetate grumeleuse is smashed to pieces, used high temperature oven to burn, remove remaining moisture and most organism, obtain nickel acid manganese powder body 400 ℃ of bakings of carrying out 4 hours.Ground about 20 minutes, the range estimation diameter of particle is no more than 1mm, continue to use high temperature oven 850 ℃ down baking burnt 6 hours, obtain particle diameter less, do not have a remaining organic manganese oxide powder.
5. make plain embryo.Ball milling 8 hours, it is last less than 1 micron nickel acid manganese powder to obtain median size.Get the 60g powder, add the polyvinyl alcohol solution of mass ratio 5%-8%, granulation.Put into mould, the static pressure pressed of 40-60Mpa 40 minutes, obtaining diameter was 78mm, and thickness is about the plain embryo of 4mm.
6. segmentation is come unstuck.Use high temperature oven to carry out segmentation and come unstuck, 100 ℃ one hour, 200 ℃ one hour, 300 ℃ one hour, 400 ℃ one hour, 500 ℃ two hours, remove the Z 150PH in the plain embryo.High temperature sintering.Segmentation is warmed up to 1050 ℃ after coming unstuck and accomplishing in High Temperature Furnaces Heating Apparatus, be incubated 8 hours.Naturally take out the cooling back, obtains the target diameter and be about 65.40mm, and pyrocondensation is than being (78-65.4)/78=16.2%, and density is 3.5gcm
-3, cutting obtains the target of diameter 61mm.Use sand papering, polishing.
Claims (1)
1. spinel structure Mn oxide (Mn
xNi
1-x) (Mn
yCo
1-y)
2O
4The thermosensitive film magnetron sputtering is characterized in that with the preparation method of target this preparing method's concrete steps are following:
(1) acetate powder of weighing manganese, cobalt, nickel: for target components is (Mn
xNi
1-x) (Mn
yCo
1-y)
2O
4Mn oxide, in four water acetic acid manganese: Cobalt diacetate tetrahydrate: the mass ratio of four water acetic acid nickel is (245.09 (x+2y)): (249.08 (2-2y)): the ratio of (248.71 (1-x)) takes by weighing acetate;
(2) use the aqueous solution of acetic acid that powder is dissolved, the ratio that adds 200ml acetic acid, 400ml water according to every 100g acetate is prepared precursor solution;
(3) precursor solution is poured in the solution splendid attire ware of negative pressure leaching machine, selecting the aperture for use is the filter membrane of 0.45 μ m, carries out negative pressure leaching, filtering small amount of impurities deposition wherein; Solution is made in the furnace pot of packing into, and oven dry obtains exsiccant acetate grumeleuse;
(4) the acetate grumeleuse is smashed to pieces; Use high temperature oven to burn 400 ℃ of bakings of carrying out 4 hours; Remove remaining moisture and most organism, ground about 20 minutes, the range estimation diameter of particle is no more than 1mm; Continue to use high temperature oven 850 ℃ down baking burnt 6 hours, obtain particle diameter less, do not have a remaining organic manganese oxide powder;
(5) ball milling is 8 hours, obtains median size less than 1 micron manganese oxide powder, adds the polyvinyl alcohol solution of mass ratio 5%-8%, and mould is put in granulation, the static pressure pressed of 40-60Mpa 40 minutes, obtains plain embryo;
(6) segmentation is come unstuck, use high temperature oven to carry out segmentation and come unstuck, 100 ℃ one hour, 200 ℃ one hour, 300 ℃ one hour, 400 ℃ one hour, 500 ℃ two hours, remove the Z 150PH in the plain embryo;
(7) high temperature sintering, segmentation are warmed up to 1050 ℃-1200 ℃ after coming unstuck and accomplishing in High Temperature Furnaces Heating Apparatus, be incubated 8 hours, and take out the cooling back naturally, cutting obtain desired size ceramic target, polish, polish, obtain sputtering target material.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI476291B (en) * | 2012-12-17 | 2015-03-11 | Nat Inst Chung Shan Science & Technology | Preparation method of spinel nickel cobalt oxide target |
| CN112259356A (en) * | 2020-10-20 | 2021-01-22 | 兰州大学 | Microwave frequency band high-permeability low-magnetic-loss alloy soft magnetic particles and preparation method thereof |
| CN114657526A (en) * | 2022-03-30 | 2022-06-24 | 长沙惠科光电有限公司 | Sputtering metal target material and preparation method and application thereof |
| CN114807882A (en) * | 2022-05-06 | 2022-07-29 | 广东省科学院半导体研究所 | Magnetron sputtering target material, preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1908229A (en) * | 2006-08-17 | 2007-02-07 | 中国科学院上海技术物理研究所 | Preparation method of manganese-cobalt-nickel thin film heat-sensitive material |
| CN102249649A (en) * | 2011-04-28 | 2011-11-23 | 华南理工大学 | Thermal sensitive ceramic and preparation method thereof |
-
2012
- 2012-05-09 CN CN2012101412245A patent/CN102650037A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1908229A (en) * | 2006-08-17 | 2007-02-07 | 中国科学院上海技术物理研究所 | Preparation method of manganese-cobalt-nickel thin film heat-sensitive material |
| CN102249649A (en) * | 2011-04-28 | 2011-11-23 | 华南理工大学 | Thermal sensitive ceramic and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI476291B (en) * | 2012-12-17 | 2015-03-11 | Nat Inst Chung Shan Science & Technology | Preparation method of spinel nickel cobalt oxide target |
| CN112259356A (en) * | 2020-10-20 | 2021-01-22 | 兰州大学 | Microwave frequency band high-permeability low-magnetic-loss alloy soft magnetic particles and preparation method thereof |
| CN114657526A (en) * | 2022-03-30 | 2022-06-24 | 长沙惠科光电有限公司 | Sputtering metal target material and preparation method and application thereof |
| CN114807882A (en) * | 2022-05-06 | 2022-07-29 | 广东省科学院半导体研究所 | Magnetron sputtering target material, preparation method and application thereof |
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Application publication date: 20120829 |