CN1908229A - Preparation method of manganese-cobalt-nickel thin film heat-sensitive material - Google Patents
Preparation method of manganese-cobalt-nickel thin film heat-sensitive material Download PDFInfo
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- CN1908229A CN1908229A CN 200610030144 CN200610030144A CN1908229A CN 1908229 A CN1908229 A CN 1908229A CN 200610030144 CN200610030144 CN 200610030144 CN 200610030144 A CN200610030144 A CN 200610030144A CN 1908229 A CN1908229 A CN 1908229A
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Abstract
The invention discloses a new preparing method of MnCoNi film material through wetting-chemical method, which is characterized by the following: enlarging area at lower temperature; stabilizing the heat-sensitive material of MnCoNi film; breaking the limit of traditional ceramic element to satisfy the request of aviation and astronautic technological element.
Description
Technical field
The present invention relates to thin film heat-sensitive material, specifically be meant the preparation method of manganese cobalt nickel (MnCoNi) thin film heat-sensitive material.
Technical background
Negative temperature coefficient (NTC) thermistor material is meant that resistance value is the material that exponential relationship reduces with the temperature rising.Thermistor occupies very important position in temperature-sensing element, almost account for 40% of whole temperature sensing element total amount.The resistance-temperature characteristics of NTC thermo-sensitive material can make small temperature variation be transformed into changes in resistance and form big signal output, is particularly suitable for high-acruracy survey.The NTC thermistor material is applied to different fields as important temperature-sensing element.
Containing galaxite is the foundation stone that the NTC thermistor material has become the NTC material.The spinel series metal oxide is locked as several oxidation of interim metal and the combination thereof based on Mn, Co, Ni etc. basically.The Mn-Co-Ni-O spinel is with its big temperature coefficient of resistance, stable performance, and broad use warm area has obtained very fast development, at aspects such as thermal-sensitive electric resistance devices wide application prospect is arranged.The MnCoNi material is to use the earliest and the highest infrared temperature-sensitive detecting material of temperature coefficient of resistance of successful Application, also is unique a kind of all wave band temperature-sensitive radiation detection material of finding at present.Have the extremely broad photoresponse wave band of 200nm-50 μ m with its prepared device, highly sensitive, time constant is little, the life-span is long and advantages of cheap price.
The MnCoNi ternary system can be understood as NiMn
2O
4, MnCo
2O
4Two kinds of sosoloid systems that spinel is formed are because above-mentioned binary spinel has close lattice parameter, so their solid solutions well.Existing MnCoNi material is to adopt traditional high-temperature sintering process preparation, is controlled at sintering under air or the nearly oxidizing atmosphere, can obtain stupalith.Usually manganese oxide, cobalt oxide and three kinds of oxide compounds of nickel oxide are pressed certain proportioning mixed pressuring plate, then at 1100～1200 ℃ of following sintering, the material shortcoming that this method is produced is homogeneity, repeatability, poor stability.The device yield of this material preparation is low, all has wretched insufficiency at aspects such as work-ing life of device and reliabilities, so its device performance also is stuck in level decades ago, can not satisfy the requirement of contemporary aeronautical and space technology development.Thereby need new breakthrough be arranged from the preparation method, just can significantly improve and improve the performance of MnCoNi material.
Summary of the invention
Purpose of the present invention is exactly the traditional MnCoNi preparation technology of Gonna breakthrough, proposes the method that a kind of new employing wet chemistry method low temperature prepares MnCoNi thin-film thermistor material.
MnCoNi thin-film thermistor material preparation method step of the present invention is as follows:
1. the preparation of precursor solution:
Solute adopts has good solubility, manganese acetate, Cobaltous diacetate, the nickel acetate of soluble in water and organic solvent, and its proportioning is Mn: Co: Ni=47-57: 29-35: 14-18 (atomic ratio), solvent uses Glacial acetic acid.
Above-mentioned acetate weighed up in proportion be dissolved in the Glacial acetic acid, heat this solution to 30～60 ℃, and constantly stir and dissolve fully, be cooled to room temperature at last until acetate.Owing to itself crystal water is just arranged in the acetate, so precursor solution contains water, and precursor solution concentration can be regulated according to the needs of single film layer thickness.
2. the preparation of film:
The above-mentioned precursor solution for preparing is dripped on the substrate, with sol evenning machine solution is evenly thrown away, even glue speed is 2000～4000 rev/mins, and the time is 15-30 second, and even glue obtains wet film; Place quick anneal oven to heat-treat with substrate wet film then, condition is: be warming up to 150～250 ℃ and kept 5-10 minute; Being warming up to 400～700 ℃ from 150～250 ℃ again kept 6-10 minute; Repeat even glue of above-mentioned spin coating and heat treatment process, until the film that obtains desired thickness.Said substrate can be Si, SiO
2, Al
2O
3, ZrO
2Deng.
Preparation method of the present invention has following positively effect and advantage:
1. adopt wet chemistry method to prepare the MnCoNi thin-film material, compare, have good uniformity, the advantage of material densification with the traditional preparation process MnCoNi stupalith method of high temperature sintering oxide powder mixture.Because the presoma that uses is a solution transparent, homogeneous, so raw material is the mixing fully in molecular level, thereby the MnCoNi film of preparing also is uniformly, and this stability to the device performance that uses this material preparation is very important.Adopt the precursor solution of this method preparation stable, not perishable.
2. the raw material of Shi Yonging is an acetate, and solvent is an acetic acid, owing to itself crystal water is just arranged in the acetate, so there is not the problem that produces hydrolytic spoilage in precursor solution, can place for a long time under the condition of normal temperature and pressure.The precursor solution compound method is simple, does not need technologies such as nitrogen protection, has simplified preparation steps, reduces cost.
3. the thermal treatment temp of film is between 400～700 ℃, and it is significantly to have reduced that the sintering temperature of comparing 1100～1200 ℃ of traditional ceramics materials is compared.Growth material in lower temperature range can be prepared the MnCoNi film of even compact, and method and silicon technology compatibility are convenient to integrated.
4. substrate selects limitation little, can be at Si, SiO
2, Al
2O
3, ZrO
2Grow the big area film forming etc. on the multiple substrate.The diversity of substrate can enlarge the range of application of device, improves the universality of material.
5. the MnCoNi sheet resistance temperature factor prepared of the present invention can be up to 3.4%/℃, the material structure densification, stability substantially exceeds the traditional ceramics material, and film sample is placed on that continuous 24 months its physical function parameters do not change in the air.
Description of drawings
Fig. 1 is the blending process figure of precursor solution;
Fig. 2 is the preparation technology figure of film.
Embodiment
Provide one to study the most preferred embodiment that obtains by experiment below, and the present invention is described in further detail.
Most preferred embodiment:
Acetate proportioning Mn: Co: Ni=52: 32: 16 (atomic ratio), solvent uses Glacial acetic acid, as long as its content makes the acetate dissolving, the size of solvent is relevant with even glue single film layer thickness.
Annealing conditions is: be warming up to 180 ℃ and kept 300 seconds in 10 seconds;
Being warming up to 500 ℃ from 180 ℃ in 10 seconds kept 400 seconds.
The sheet resistance temperature factor that finally obtains up to 3.4%/℃.
In the preparation process of the present invention, the precursor solution quality of preparation will directly influence the film quality of being grown, and consider the influence to human body when choosing raw material, select the raw material of nontoxic or low toxicity as far as possible.It is starting raw material that the present invention chooses manganese acetate, Cobaltous diacetate, nickel acetate, and acetate has good solubility, soluble in water and organic solvent.Usually acetate contains certain crystal water, need not remove crystal water in the present invention, has the simple advantage of blending process, as raw material, does not need nitrogen protection than organometallics, simplifies preparation technology.In addition, the present invention uses Glacial acetic acid as solvent, and does not use ether solvent, reduces the murder by poisoning to human body.
In the process of preparation film, the selection of annealing temperature and annealing time also is very important, because annealing time is too high or annealing time is long, all can cause the negative reaction that reduces film quality.Study us by experiment and selected suitable annealing temperature and time, make film crystallization film forming and have required excellent properties.Wet film is pyrolysis at a lower temperature, removes organism, then crystallization under comparatively high temps.
Claims (1)
1. the preparation method of a manganese-cobalt-nickel thin film heat-sensitive material is characterized in that concrete steps are as follows:
A. the preparation of precursor solution:
Solute adopts manganese acetate, Cobaltous diacetate, nickel acetate, and its proportioning is Mn: Co: Ni=47-57: 29-35: 14-18 (atomic ratio), and solvent uses Glacial acetic acid;
Acetate weighed up according to the above ratio be dissolved in the Glacial acetic acid, heat this solution to 30～60 ℃, and constantly stir and dissolve fully, be cooled to room temperature at last until acetate; The concentration of precursor solution can be regulated according to the needs of single film layer thickness;
B. the preparation of film:
The above-mentioned precursor solution for preparing is dripped on the substrate, with sol evenning machine solution is evenly thrown away, even glue speed is 2000～4000 rev/mins, and the time is 15-30 second, and even glue obtains wet film; Place quick anneal oven to heat-treat with substrate wet film then, condition is: be warming up to 150～250 ℃ and kept 5-10 minute; Being warming up to 400～700 ℃ from 150～250 ℃ again kept 6-10 minute; Repeat even glue of above-mentioned spin coating and heat treatment process, until the film that obtains desired thickness.
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|---|---|---|---|
| CNB2006100301447A CN100443631C (en) | 2006-08-17 | 2006-08-17 | Preparation method of manganese-cobalt-nickel thin film heat-sensitive material |
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|---|---|---|---|
| CNB2006100301447A CN100443631C (en) | 2006-08-17 | 2006-08-17 | Preparation method of manganese-cobalt-nickel thin film heat-sensitive material |
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| CN1908229A true CN1908229A (en) | 2007-02-07 |
| CN100443631C CN100443631C (en) | 2008-12-17 |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102249649A (en) * | 2011-04-28 | 2011-11-23 | 华南理工大学 | Thermal sensitive ceramic and preparation method thereof |
| CN102503376A (en) * | 2011-11-10 | 2012-06-20 | 中国科学院上海技术物理研究所 | Preparation method of manganese cobalt nickel thermosensitive ceramic material |
| CN102593242A (en) * | 2012-03-22 | 2012-07-18 | 中国科学院上海技术物理研究所 | Manufacturing method of wideband film type photoelectric detector with Pt/Ti/SiO2/Si substrate |
| CN102593228A (en) * | 2012-04-20 | 2012-07-18 | 中国科学院上海技术物理研究所 | Wide-waveband thin-film type photoelectric detector based on Pt/Ti/SiO2/Si substrate |
| CN102650037A (en) * | 2012-05-09 | 2012-08-29 | 中国科学院上海技术物理研究所 | Method for manufacturing magnetron sputtering target material of Mn-Co-Ni-O thin film |
| CN102732848A (en) * | 2012-06-25 | 2012-10-17 | 中国科学院上海技术物理研究所 | Method for preparing single oriented manganese cobalt nickel oxygen film by magnetron sputtering |
| CN102775133A (en) * | 2012-06-25 | 2012-11-14 | 中国科学院上海技术物理研究所 | Method for rapidly preparing Mn-Co-Ni-O polycrystal thick films |
| CN106048527A (en) * | 2016-06-12 | 2016-10-26 | 中国科学院上海技术物理研究所 | Method for preparing flexible thermosensitive film material |
| CN106835081A (en) * | 2017-02-28 | 2017-06-13 | 宁夏大学 | The preparation method of NTC thermosensitive material films |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2676469B2 (en) * | 1993-04-23 | 1997-11-17 | 株式会社芝浦電子 | Method for manufacturing NTC thermistor |
| CN1046052C (en) * | 1996-12-14 | 1999-10-27 | 中国科学院新疆物理研究所 | Oxidate semi-conductor thermosensitive resistance and mfg. method thereof |
| JPH11323568A (en) * | 1998-05-13 | 1999-11-26 | Murata Mfg Co Ltd | Plating liquid and production of ceramic electronic part using that |
| CN1092390C (en) * | 1998-10-08 | 2002-10-09 | 中国科学院新疆物理研究所 | Sol-gel process for preparing thermosensitive film resistor with negative temp. coefficient |
| CN100386473C (en) * | 2005-09-08 | 2008-05-07 | 陕西科技大学 | Collosol/gel preparation method for Sm2O3 photoelectric film |
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2006
- 2006-08-17 CN CNB2006100301447A patent/CN100443631C/en active Active
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102249649A (en) * | 2011-04-28 | 2011-11-23 | 华南理工大学 | Thermal sensitive ceramic and preparation method thereof |
| CN102503376A (en) * | 2011-11-10 | 2012-06-20 | 中国科学院上海技术物理研究所 | Preparation method of manganese cobalt nickel thermosensitive ceramic material |
| CN102593242A (en) * | 2012-03-22 | 2012-07-18 | 中国科学院上海技术物理研究所 | Manufacturing method of wideband film type photoelectric detector with Pt/Ti/SiO2/Si substrate |
| CN102593228A (en) * | 2012-04-20 | 2012-07-18 | 中国科学院上海技术物理研究所 | Wide-waveband thin-film type photoelectric detector based on Pt/Ti/SiO2/Si substrate |
| CN102650037A (en) * | 2012-05-09 | 2012-08-29 | 中国科学院上海技术物理研究所 | Method for manufacturing magnetron sputtering target material of Mn-Co-Ni-O thin film |
| CN102732848A (en) * | 2012-06-25 | 2012-10-17 | 中国科学院上海技术物理研究所 | Method for preparing single oriented manganese cobalt nickel oxygen film by magnetron sputtering |
| CN102775133A (en) * | 2012-06-25 | 2012-11-14 | 中国科学院上海技术物理研究所 | Method for rapidly preparing Mn-Co-Ni-O polycrystal thick films |
| CN102732848B (en) * | 2012-06-25 | 2014-07-30 | 中国科学院上海技术物理研究所 | Method for preparing single oriented manganese cobalt nickel oxygen film by magnetron sputtering |
| CN106048527A (en) * | 2016-06-12 | 2016-10-26 | 中国科学院上海技术物理研究所 | Method for preparing flexible thermosensitive film material |
| CN106048527B (en) * | 2016-06-12 | 2018-06-29 | 中国科学院上海技术物理研究所 | A kind of method for preparing flexible thermosensitive material film |
| CN106835081A (en) * | 2017-02-28 | 2017-06-13 | 宁夏大学 | The preparation method of NTC thermosensitive material films |
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