CN111029065A - High-precision and high-reliability Ir-Cu-Au composite electrode thermosensitive chip - Google Patents

High-precision and high-reliability Ir-Cu-Au composite electrode thermosensitive chip Download PDF

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CN111029065A
CN111029065A CN201911412998.5A CN201911412998A CN111029065A CN 111029065 A CN111029065 A CN 111029065A CN 201911412998 A CN201911412998 A CN 201911412998A CN 111029065 A CN111029065 A CN 111029065A
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layer
chip
thermosensitive
ceramic substrate
thickness
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贺晓东
许志勇
段兆祥
杨俊�
唐黎民
柏琪星
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Exsense Electronics Technology Co ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01CRESISTORS
    • H01C7/00Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
    • H01C7/008Thermistors
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01CRESISTORS
    • H01C1/00Details
    • H01C1/14Terminals or tapping points or electrodes specially adapted for resistors; Arrangements of terminals or tapping points or electrodes on resistors
    • H01C1/1413Terminals or electrodes formed on resistive elements having negative temperature coefficient
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01CRESISTORS
    • H01C1/00Details
    • H01C1/14Terminals or tapping points or electrodes specially adapted for resistors; Arrangements of terminals or tapping points or electrodes on resistors
    • H01C1/142Terminals or tapping points or electrodes specially adapted for resistors; Arrangements of terminals or tapping points or electrodes on resistors the terminals or tapping points being coated on the resistive element
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01CRESISTORS
    • H01C17/00Apparatus or processes specially adapted for manufacturing resistors
    • H01C17/006Apparatus or processes specially adapted for manufacturing resistors adapted for manufacturing resistor chips
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01CRESISTORS
    • H01C17/00Apparatus or processes specially adapted for manufacturing resistors
    • H01C17/28Apparatus or processes specially adapted for manufacturing resistors adapted for applying terminals
    • H01C17/288Apparatus or processes specially adapted for manufacturing resistors adapted for applying terminals by thin film techniques
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01CRESISTORS
    • H01C7/00Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
    • H01C7/04Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having negative temperature coefficient
    • H01C7/042Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having negative temperature coefficient mainly consisting of inorganic non-metallic substances

Abstract

The invention relates to a high-precision and high-reliability Ir-Cu-Au composite electrode thermosensitive chip which comprises a thermosensitive ceramic substrate and two composite electrodes arranged on two surfaces of the thermosensitive ceramic substrate respectively, wherein each composite electrode is formed by sequentially laminating an iridium layer, a copper layer and a gold layer on the surface of the thermosensitive ceramic substrate from inside to outside. The invention also relates to a preparation method of the thermosensitive chip. The thermosensitive chip has the advantages of good stability, high reliability, difficult aging, cold and thermal shock resistance and the like.

Description

High-precision and high-reliability Ir-Cu-Au composite electrode thermosensitive chip
Technical Field
The invention relates to the technical field of thermistors, in particular to a high-precision and high-reliability Ir-Cu-Au composite electrode thermosensitive chip.
Background
The thermistor chip, referred to as a thermistor chip for short, is widely applied to various temperature detection, temperature compensation and temperature control circuits, and plays a core role in converting temperature variables into required electronic signals in the circuits.
As shown in fig. 1, the conventional thermal chip includes a thermal ceramic substrate 1 'and two metal electrodes 2' respectively disposed on two surfaces of the thermal ceramic substrate 1 ', wherein the metal electrodes 2' are typically silver electrodes. The existing preparation process of the thermosensitive chip comprises the following steps: thermal sensitive ceramic powder material preparation → ball milling → isostatic compaction → sintering ceramic ingot → slicing → silk screen printing silver paste → drying → silver burning → cutting.
However, the use of silver electrodes and the use of screen printing have several problems:
1) silver paste is easily polluted in the screen printing and drying processes, and the obtained silver electrode is also easily oxidized, yellowed and blackened, so that the stability and reliability of the product are poor;
2) the procedures of preparing silver paste in the early stage, drying the silver paste in the later stage and sintering the silver electrode are more complicated;
3) the printed silver electrode layer is large in thickness and uneven in coverage on the surface of the thermosensitive ceramic substrate, peeling and burrs are easy to generate in the cutting process, and the loss of silver paste materials is high;
4) the silver layer is recrystallized during high-temperature sintering, and the crystal form is changed, so that the performance is changed, and the electrical performance of the product is reduced;
5) the gas discharged in the high-temperature silver burning process pollutes the environment.
Disclosure of Invention
Based on the structure, the invention provides the high-precision and high-reliability Ir-Cu-Au composite electrode thermosensitive chip which has the advantages of good stability, high reliability, difficult aging, cold and thermal shock resistance and the like.
The technical scheme adopted by the invention is as follows:
the high-precision and high-reliability Ir-Cu-Au composite electrode thermosensitive chip comprises a thermosensitive ceramic substrate and two composite electrodes which are respectively arranged on two surfaces of the thermosensitive ceramic substrate, wherein the composite electrodes are formed by sequentially laminating an iridium layer, a copper layer and a gold layer on the surface of the thermosensitive ceramic substrate from inside to outside.
The heat-sensitive chip adopts the iridium-Cu-Au composite electrode, wherein the iridium layer (Ir) is used as a bottom electrode and mainly plays a role in transition, can be well combined with the heat-sensitive ceramic substrate and the copper layer, plays a certain role in blocking, can resist higher temperature, has high chemical stability, and can ensure that the function of the whole electrode is not influenced even if the copper layer and the gold layer outside are corroded; the copper layer (Cu) is used as a barrier layer for blocking the external damage to the transition layer and has a welding effect; the gold layer (Au) is a welding layer and a protective layer, has high stability, and can prevent oxidation, corrosion, damage and high temperature.
According to the invention, the iridium layer, the copper layer and the gold layer are laminated from inside to outside to form the composite electrode on the surface of the thermosensitive ceramic substrate, so that the stability, temperature resistance, corrosion resistance and damage resistance of the thermosensitive chip can be effectively improved, the reliability is obviously improved, the electrode material cost of the chip can be controlled, and the thermosensitive chip has the advantages of good stability, high reliability, difficult aging and cold and thermal shock resistance.
Specifically, the thickness of the iridium layer is 0.01-2 microns.
Specifically, the thickness of the copper layer is 0.01-2 microns.
Specifically, the thickness of the gold layer is 0.01-1 micron.
In the composite electrode, the cost is increased when the thickness of each metal layer is too thick, the combination of the composite electrode and the thermosensitive ceramic substrate is influenced when the iridium layer serving as the transition layer is too thin, the copper layer serving as the barrier layer cannot play a role in blocking when the copper layer is too thin, and the barrier layer is easily damaged by the outside when the gold layers serving as the welding layer and the protective layer are too thin, so that the reliability of the product is influenced.
Further, the thickness of the iridium layer is 0.35 micrometer, the thickness of the copper layer is 0.45 micrometer, and the thickness of the gold layer is 0.2 micrometer. This thickness setting is preferred.
Specifically, the iridium layer, the copper layer and the gold layer are all formed by a sputtering method. The thickness of each metal layer obtained by the sputtering process can reach 1% of the thickness of the silver electrode layer prepared by the screen printing process, the metal material is saved, harmful gas emission during silver burning can be avoided, the environment-friendly effect is achieved, the composite electrode is tightly attached to the thermosensitive ceramic substrate by the sputtering process, and the peeling phenomenon is basically avoided in the subsequent cutting process.
The invention also provides a preparation method of the thermosensitive chip, which comprises the following steps: preparing a thermal sensitive ceramic substrate, respectively sputtering an iridium layer, a copper layer and a gold layer on two surfaces of the thermal sensitive ceramic substrate in sequence, and then cutting to obtain a single thermal sensitive chip.
The preparation method adopts the sputtering process to prepare the electrode, the thickness of each metal layer obtained by the sputtering process can reach 1% of the thickness of the silver electrode layer prepared by the screen printing process, the function of saving metal materials is achieved, the whole sputtering process is completed in vacuum equipment, the generation of harmful gas during silver burning can be avoided, the environment cannot be polluted, the cleanliness is high, the subsequent drying and sintering processes of preparing the silver electrode layer by the screen printing are omitted, the efficiency is higher, and the performance change caused by recrystallization of each metal layer during high-temperature sintering is avoided. The metal layers obtained by the sputtering process are very compact and firm in combination, can effectively prevent external erosion, and achieves high precision and high reliability.
Further, the method also comprises the step of cleaning the heat-sensitive ceramic substrate before sputtering. The vacuum sputtering process can ensure that the cleaning surface of the thermal sensitive ceramic substrate is not secondarily polluted,
for a better understanding and practice, the invention is described in detail below with reference to the accompanying drawings.
Drawings
FIG. 1 is a schematic structural diagram of a conventional thermal chip;
FIG. 2 is a schematic structural diagram of a composite electrode thermosensitive chip according to the present invention;
FIG. 3 is a flow chart of the preparation of the composite electrode thermosensitive chip of the present invention;
fig. 4 is a schematic view of vacuum sputtering.
Detailed Description
Please refer to fig. 2, which is a schematic structural diagram of a composite electrode thermal chip according to the present invention.
The composite electrode thermosensitive chip comprises a thermosensitive ceramic substrate 1 and two composite electrodes 2 respectively arranged on two surfaces of the thermosensitive ceramic substrate 1, wherein the composite electrodes 2 are formed by sequentially laminating an iridium layer 21, a copper layer 22 and a gold layer 23 on the surface of the thermosensitive ceramic substrate 1 from inside to outside.
Specifically, the thickness of the iridium layer 21 is 0.01-2 microns; the thickness of the copper layer 22 is 0.01-2 microns; the thickness of the gold layer 23 is 0.01-1 micron. Preferably, the thickness of the iridium layer 21 is 0.35 micrometers, the thickness of the copper layer 22 is 0.45 micrometers, and the thickness of the gold layer 23 is 0.2 micrometers.
The iridium layer 21, the copper layer 22 and the gold layer 23 are formed by a sputtering method.
Referring to fig. 3 and 4, fig. 3 is a flow chart of the preparation of the composite electrode thermosensitive chip of the present invention, and fig. 4 is a schematic view of vacuum sputtering.
The preparation method of the composite electrode thermosensitive chip is carried out according to the following steps:
s1: preparing a heat-sensitive ceramic substrate:
preparing thermosensitive ceramic powder such as NTC thermosensitive ceramic powder according to a conventional formula, and performing ball milling, isostatic pressing, sintering and slicing on the thermosensitive ceramic powder to obtain the flaky thermosensitive ceramic substrate.
S2: primary cleaning:
and (4) treating the thermosensitive ceramic substrate obtained in the step S1 by using a cleaning solution, and cleaning by using an ultrasonic machine, wherein the cleaning time is as follows: 5 +/-1 min, and then drying at the drying temperature: 100 +/-5 ℃, and the drying time is as follows: 30 + -5 minutes.
S3: secondary cleaning:
and (4) placing the thermal sensitive ceramic substrate obtained by the primary cleaning in the step (S2) into a plasma cleaning machine for secondary cleaning, wherein the cleaning time is as follows: 5 +/-1 min, and the drying temperature is as follows: 100 +/-5 ℃, and the drying time is as follows: 30 ± 5 minutes while activating the surface.
S4: sputtering an iridium layer 21:
firstly, a vacuum sputtering film plating machine is vacuumized to a process range, argon is filled as a working gas, iridium is used as a target material, and Ar is applied under the action of an electric field+And (4) accelerating bombardment of the target, sputtering target atoms onto the thermal sensitive ceramic base material obtained in the step S3, and respectively sputtering an iridium layer 21 on two surfaces of the thermal sensitive ceramic base material, wherein the sputtering thickness is 0.01-2 microns.
S5: sputtering of the copper layer 22:
firstly, a vacuum sputtering film plating machine is vacuumized to a process range, argon is filled as a working gas, copper is used as a target material, and Ar is generated under the action of an electric field+And (4) accelerating bombardment of the target, sputtering target atoms onto the thermal sensitive ceramic base material obtained in the step S4, and respectively sputtering a copper layer 22 on the iridium layer 21 on the two surfaces of the thermal sensitive ceramic base material, wherein the sputtering thickness is 0.01-2 microns.
S6: sputtering of a gold layer 23:
firstly, a vacuum sputtering film plating machine is vacuumized to a process range, argon is filled as a working gas, gold is used as a target material, and Ar is applied under the action of an electric field+And (4) accelerating bombardment of the target, sputtering target atoms onto the thermosensitive ceramic substrate obtained in the step S5, and respectively sputtering a gold layer 23 on the surfaces of the copper layers 22 on the two surfaces of the thermosensitive ceramic substrate, wherein the sputtering thickness is 0.01-1 micron.
S7: cutting-up
And (4) testing the resistivity of the thermosensitive ceramic substrate obtained in the step (S6), calculating the size of a single thermosensitive chip according to the test result and the resistance value of the required thermosensitive chip, and then cutting the thermosensitive ceramic substrate to obtain the single thermosensitive chip.
S8: testing and sorting:
and (4) using the thermistor tester 3 to test the resistance values of the thermistor chips obtained by batch production in the step S7 one by one, and sorting and eliminating products which do not meet the requirements.
Performance comparison test of existing thermosensitive chip and composite electrode thermosensitive chip
Respectively manufacturing a ceramic substrate with the resistivity of 75k omega-mm, the B value of 4050 and the thickness of 0.5mm by using a traditional screen printing method and a vacuum sputtering method to manufacture a surface electrode of the ceramic substrate; wherein, the screen printing method is used for respectively manufacturing silver electrodes with the thickness of 30 mu m on the two surfaces of the ceramic substrate; the vacuum sputtering method is used for manufacturing composite electrodes formed by laminating an iridium layer, a copper layer and a gold layer from inside to outside on two surfaces of a ceramic substrate respectively (the vacuum degree of the sputtered iridium layer is 0.4Pa, and the vacuum degrees of the sputtered copper layer and the gold layer are both 0.3Pa), wherein the thickness of the iridium layer is 0.35 mu m, the thickness of the copper layer is 0.45 mu m, and the thickness of the gold layer is 0.2 mu m. Then, the current thermosensitive chip prepared by a silk-screen method and the composite electrode thermosensitive chip prepared by a vacuum sputtering method are obtained by cutting according to the size of 1mm by 1 mm.
The resistance values and B values of the conventional thermosensitive chip obtained by cutting and the thermosensitive chip with the composite electrode are respectively tested, a high-temperature aging experiment at 125 ℃/1000H and a cold-hot impact experiment at 100-0 ℃ are respectively carried out, and 10 samples are adopted in each experiment.
The high temperature aging test is as follows: and (3) aging the sample in a 125 ℃ oven for 1000 hours, and calculating the resistance change rate according to the resistance values of the sample at 25 ℃ before and after the experiment, namely the aging change rate.
The cold and hot impact test is as follows: and (3) alternately placing the samples in gas at 100 ℃ and 0 ℃, circulating for 1000 times, and calculating the resistance change rate at 25 ℃ according to the resistance of the samples before and after the experiment, namely the cold and hot shock change rate.
The results of the experiment are as follows:
Figure BDA0002350455450000051
the data in the table show that the resistance value and the B value of the conventional thermosensitive chip are relatively dispersed, the precision is relatively low, the aging change rate and the cold-heat shock change rate are relatively high, and the reliability is relatively low; the resistance value and the B value of the composite electrode thermosensitive chip are very concentrated, the precision is high, the aging change rate is not more than 0.28%, the cold and hot shock change rate is not more than 0.2%, and high precision, high reliability are achieved.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.

Claims (8)

1. A high-precision and high-reliability Ir-Cu-Au composite electrode thermosensitive chip is characterized in that: the composite electrode is formed by sequentially laminating an iridium layer, a copper layer and a gold layer on the surface of the thermal sensitive ceramic substrate from inside to outside.
2. A thermal chip as recited in claim 1, wherein: the thickness of the iridium layer is 0.01-2 microns.
3. A thermal chip as recited in claim 1, wherein: the thickness of the copper layer is 0.01-2 microns.
4. A thermal chip as recited in claim 1, wherein: the thickness of the gold layer is 0.01-1 micron.
5. A thermal chip as recited in claim 1, wherein: the thickness of iridium layer is 0.35 micron, the thickness of copper layer is 0.45 micron, the thickness of gold layer is 0.2 micron.
6. The thermal chip according to any one of claims 1 to 5, wherein: the iridium layer, the copper layer and the gold layer are all formed by a sputtering method.
7. The method for producing a thermosensitive chip according to claim 1, wherein: the method comprises the following steps: preparing a thermal sensitive ceramic substrate, respectively sputtering an iridium layer, a copper layer and a gold layer on two surfaces of the thermal sensitive ceramic substrate in sequence, and then cutting to obtain a single thermal sensitive chip.
8. The method of claim 7, wherein: the method also comprises the step of cleaning the heat-sensitive ceramic substrate before sputtering.
CN201911412998.5A 2019-12-31 2019-12-31 High-precision and high-reliability Ir-Cu-Au composite electrode thermosensitive chip Pending CN111029065A (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1367497A (en) * 2001-01-26 2002-09-04 奠基石传感器公司 Thermistor and its production method
JP2007141881A (en) * 2005-11-14 2007-06-07 Oizumi Seisakusho:Kk Electrode structure of thermistor
CN102800449A (en) * 2012-07-26 2012-11-28 东莞市东思电子技术有限公司 Chip thermistor and manufacturing method thereof
CN109461556A (en) * 2018-11-15 2019-03-12 中国科学院新疆理化技术研究所 A kind of preparation method of the Ohm contact electrode of p-type negative temperature coefficient ceramics material
CN209118860U (en) * 2018-12-29 2019-07-16 广东爱晟电子科技有限公司 A kind of highly reliable Ti-Cu-Au combination electrode heat sensitive chip of high-precision
CN210182176U (en) * 2019-08-30 2020-03-24 唐山恭成科技有限公司 Sn-Ni-Ag composite electrode thermistor chip

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1367497A (en) * 2001-01-26 2002-09-04 奠基石传感器公司 Thermistor and its production method
JP2007141881A (en) * 2005-11-14 2007-06-07 Oizumi Seisakusho:Kk Electrode structure of thermistor
CN102800449A (en) * 2012-07-26 2012-11-28 东莞市东思电子技术有限公司 Chip thermistor and manufacturing method thereof
CN109461556A (en) * 2018-11-15 2019-03-12 中国科学院新疆理化技术研究所 A kind of preparation method of the Ohm contact electrode of p-type negative temperature coefficient ceramics material
CN209118860U (en) * 2018-12-29 2019-07-16 广东爱晟电子科技有限公司 A kind of highly reliable Ti-Cu-Au combination electrode heat sensitive chip of high-precision
CN210182176U (en) * 2019-08-30 2020-03-24 唐山恭成科技有限公司 Sn-Ni-Ag composite electrode thermistor chip

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