CN110265539B - Processing method of copper-nickel alloy film thermocouple - Google Patents
Processing method of copper-nickel alloy film thermocouple Download PDFInfo
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- CN110265539B CN110265539B CN201910453155.3A CN201910453155A CN110265539B CN 110265539 B CN110265539 B CN 110265539B CN 201910453155 A CN201910453155 A CN 201910453155A CN 110265539 B CN110265539 B CN 110265539B
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/01—Manufacture or treatment
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/10—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects
- H10N10/17—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects characterised by the structure or configuration of the cell or thermocouple forming the device
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
- H10N10/81—Structural details of the junction
- H10N10/817—Structural details of the junction the junction being non-separable, e.g. being cemented, sintered or soldered
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N19/00—Integrated devices, or assemblies of multiple devices, comprising at least one thermoelectric or thermomagnetic element covered by groups H10N10/00 - H10N15/00
- H10N19/101—Multiple thermocouples connected in a cascade arrangement
Abstract
The invention provides a method for processing a copper-nickel alloy film thermocouple. The invention carries out copper-nickel alloy film processing on a special insulating base material, processes a single copper-nickel alloy-copper connected metal module for temperature measurement into a continuous film by a thermocouple, and carries out multilayer lamination according to actual requirements. Under the same temperature measurement condition, the measured potential difference is multiplied, and the result of accurately detecting the tiny temperature difference can be realized. The invention also interconnects the insulating substrates of the modified film thermocouple in a multilayer manner, realizes the series connection of a plurality of thermocouples, realizes the detection of micro temperature difference, and can be used for the detection of temperature difference requiring higher sensitivity.
Description
Technical Field
The invention belongs to the field of semiconductor devices, and relates to a processing method of a copper-nickel alloy film thermocouple and application of the film thermocouple in the field of precise temperature measurement.
Background
In various fields such as industrial production, aerospace, and electric heating instruments, temperature monitoring, adjustment, and control are indispensable, and among them, temperature detection is generally performed by using a thermoelectric phenomenon. In general, the temperature measurement can be performed by directly contacting the measured substance, and in the case of difficult or inconvenient acquisition, the temperature measurement can be performed by using a non-contact method. The thermocouple is a main means of contact temperature measurement due to the advantages of wide temperature detection range, high response speed, high cost performance and the like.
The thermocouple has the following advantages:
(1) The temperature measurement accuracy is higher. The usual k-index thermocouples had a class I error range of about. + -. 0.4% and a class II error range of. + -. 0.75% by weight.
(2) The structure is relatively simple. The components comprise electrodes, wiring terminals, insulators, sheaths and the like.
(3) The dynamic response speed is high. And excessive thermal inertia is not easy to generate in the temperature measuring process.
(4) The signal can be transmitted over a long distance. The device is widely matched with a DCS system for application, and is convenient for centralized detection and automatic control.
(5) The temperature can be measured locally. The method is suitable for measuring the temperature of the fine element.
The detection characteristics of thermocouples made of different metal materials are also different, and the thermocouple materials need to be considered in many aspects such as cost and performance in consideration of the wide range of the use of thermocouple elements.
The copper-nickel alloy thermocouple can be applied at low temperature, has the temperature measurement range of-250-300 ℃, has better stability and sensitivity, low cost, high mechanical strength and good pressure resistance, can be processed into a slender shape under the existing condition, and is widely applied to the fields of industry and the like. The main characteristic description can be seen in the following table:
in thermocouple applications, the input impedance of the voltage measuring element is higher than the resistance of the thermocouple element and its extension because it is necessary to prevent excessive current flow through the loop, which may cause other pyroelectric effects or IR drop in the thermocouple element and its wire. The voltage generated by the metal thermocouple element is therefore not high, typically 10-80 μ V/C, which requires a sufficiently high resolution of the element measuring the thermocouple output.
Because the thermoelectromotive force generated by the thermocouple is only millivolt, the corresponding measuring element of the thermocouple can measure small voltage and distinguish tiny voltage change, and for a temperature measuring system or a corresponding temperature control system, if the tiny voltage change can be distinguished more precisely, the precision degree of a detection result can be greatly improved.
For a thermocouple application scenario requiring detection of a slight temperature difference, a thermocouple element capable of accurately detecting a slight temperature difference is necessary. For example, in the aerospace field, a thermocouple temperature measuring element used by an airplane distinguishes the height and air pressure data of the airplane according to temperature difference and change; for example, in the field of body temperature detection, a thermocouple temperature measuring element used by a detection sensor is used for pathological judgment or data collection by biological fine body temperature change; such as high thermal conductivity instruments, require accurate temperature change data as experimental data, etc.
In view of the foregoing, there is a need in the art for a thermocouple that can accurately detect small temperature differences and that is low in cost and can be mass produced.
Disclosure of Invention
The invention aims to provide a high-sensitivity copper-nickel alloy film thermocouple for measuring a tiny temperature difference.
The basic principle of thermocouple temperature measurement is that two different metal conductors are connected to form a loop according to the thermoelectric effect, and when temperature gradients exist at two ends, electromotive force is generated in the loop, so that current is formed, namely electromotive force-thermoelectric force exists at two ends of thermocouple temperature measurement, namely the Bezick effect.
Two metal conductors A and B of different materials are connected end to form a closed loop, such as two connection points (T) 1 ，T 2 ) On the other hand, a thermoelectric potential E (t) is generated in the circuit 1 ，t 2 ) And a thermal current is formed.
At the node of the two metals, a contact potential difference is generated as a result of electron diffusion, and the total contact potential difference of the hot and cold sides thereof is:
the two ends of the same conductor generate different potential differences due to different temperatures, and in a thermocouple loop, the total Thomson electromotive force of two metals is as follows:
the electromotive force generated by the thermocouple is composed of the total contact potential and the total thomson potential of two conductors, namely:
in summary, after the materials constituting the thermocouple are determined, the relationship between the electromotive force and the temperature difference can be expressed as follows:
E AB ＝C(t 2 -t 1 )+d(t 2 -t 1 ) 2
wherein, t 2 Is hot end temperatureDegree, t 1 Is the cold end temperature and C and d are the galvanic constants, the magnitude of which depends on the thermocouple material.
For rough measurement, a first approximation can be taken:
E AB ＝C(t 2 -t 1 )
wherein C is a thermoelectric coefficient (couple constant) which is related only to the properties of two metals constituting the thermocouple and is numerically equal to the thermoelectromotive force generated when the temperature difference between two contact points is 1 ℃ in mV/DEG C.
This patent establishes ties N group's thermocouple unit, and under the same difference in temperature condition, measurable thermoelectric force is:
E′ AB ＝C(t 2 -t 1 )·N
it can be seen that when a single thermocouple unit measures a slight temperature difference, E results because Δ t is too small AB The numerical value is too small, so that errors are easily caused or the sensitivity of the device is easily influenced; in the patent, thermocouple units are modified on the same substrate in series, multilayer substrate interconnection can be realized, and E 'can be obtained when the unit number is larger' AB The larger the temperature difference is, the more the electromotive force under the small temperature difference can be clearly measured, thereby measuring the corresponding temperature difference value or ensuring the sensitivity of the device.
The copper-nickel alloy thermocouple that this patent used, the temperature changes 10 ℃ every time, and the thermoelectric force changes about 40 mu V, uses the thin-film series connection technique that this patent provided, can rise the electromotive force change from mu V to mV at double, can rise thermocouple sensitivity at double.
The invention also aims to provide a processing method of the copper-nickel alloy thin film thermocouple.
The technical scheme adopted by the preparation method of the copper-nickel alloy film thermocouple comprises the following steps:
(1) Performing magnetron sputtering of copper-nickel alloy on the surface of the substrate;
(2) Processing an etching circuit on the surface of the substrate;
(3) Selectively covering ink on the surface of the substrate to expose the selected copper-nickel alloy area;
(4) Electroplating copper on the copper-nickel alloy area exposed on the surface of the substrate;
(5) And (4) carrying out de-inking treatment on the substrate to obtain the copper-nickel alloy thin-film thermocouple with a plurality of thermocouple units connected in series.
The substrate in the present invention may use PET, PI, PTFE, or ceramics as a base material, and the base material has an insulating property.
The ink of the present invention may be solder resist ink.
In the step (1) of the invention, the copper-nickel alloy is sputtered on the surface of the substrate by magnetron sputtering, the DPC ceramic film circuit process is adopted, the substrate is cleaned by pretreatment, and the copper-nickel alloy layer is sputtered and combined on the substrate by utilizing the film professional manufacturing technology-vacuum coating mode.
In step (1) of the present invention, the atomic fraction of nickel element in the copper-nickel alloy is 10 to 90, preferably 44.
In the step (2), an etching circuit is processed on the surface of the substrate, and the patterned circuit is manufactured by adopting the processes of exposure, development, etching and film removal. The circuit pattern processing method adopts at least one of photoresist, dry film and photosensitive ink for processing.
In the step (4) of the invention, the copper plating is copper plating by using electroplating and brush plating modes.
In step (5) of the present invention, the de-inking treatment is to remove the ink on the substrate by using a chemical etching method, and the etching solution used is an alkali solution, preferably potassium hydroxide.
The beneficial effects of the invention are:
(1) Compared with the traditional thermocouple, the thin-film thermocouple has the advantages of small time constant, high reaction speed, small heat capacity and the like, and can measure the minute temperature change at every moment more quickly and accurately.
(2) And a film continuous design is adopted, so that a plurality of thermocouple units are connected in series, and the temperature detection sensitivity is greatly improved.
(3) The thin film thermocouple is processed on the insulating substrate, so that the cost is low, the mass production is easy, the multilayer interconnection can be realized, the volume of the thermocouple element is reduced, the structure is further simplified, and the thin film thermocouple can be used for precise devices.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required to be used in the embodiments are briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present patent, and therefore should not be considered as limiting the scope, and those skilled in the art can also obtain other related drawings based on these drawings without creative efforts.
FIG. 1 is a conventional thermocouple;
FIG. 2 is a schematic diagram of magnetron sputtering a copper-nickel alloy on the surface of a substrate, and etching a circuit to remove the copper-nickel alloy outside the circuit range;
FIG. 3 is a schematic diagram of selective ink coverage on a substrate surface, exposing selected copper nickel alloy regions;
FIG. 4 is a schematic diagram of copper electroplating of exposed copper-nickel alloy areas on the substrate surface;
FIG. 5 shows a copper-nickel alloy thin film thermocouple obtained by de-inking the substrate.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples. The invention is capable of various embodiments and of modifications and variations therein. However, it should be understood that: there is no intention to limit the various embodiments of this patent to the specific embodiments disclosed herein, but on the contrary, the intention is to cover all modifications, equivalents, and/or alternatives falling within the spirit and scope of the various embodiments of the patent.
A processing method of a copper-nickel alloy film thermocouple comprises the following steps:
(1) Carrying out magnetron sputtering on the surface of the substrate to form copper-nickel alloy;
(2) Processing an etching circuit on the surface of the substrate;
(3) Selectively covering ink on the surface of the substrate to expose the selected copper-nickel alloy area;
(4) Electroplating copper on the copper-nickel alloy area exposed on the surface of the substrate;
(5) And (4) carrying out de-inking treatment on the substrate to obtain the copper-nickel alloy thin-film thermocouple with a plurality of thermocouple units connected in series.
Preferably, in the step (1), the substrate is made of: PET, PI, PTFE, ceramic, and the like.
Preferably, in the step (1), the atomic fraction of nickel element in the copper-nickel alloy is 10-90; more preferably, the atomic fraction of the nickel element in the copper-nickel alloy is 44.
Preferably, in the step (3), the solder resist ink is selected as the ink material.
Preferably, in the step (4), the copper plating is performed by electroplating or brush plating; more preferably, the copper plating is performed by electroplating.
In the step (5), the de-inking treatment is to remove the ink on the substrate by using a chemical etching method, and the used etching solution is alkali liquor.
Preferably, the alkali liquor is potassium hydroxide.
The present invention will be described in further detail with reference to specific examples.
Example 1
Processing of thermocouple for airplane detection:
as shown in fig. 2 to 5, the preparation process of the copper-nickel alloy-copper thin film thermocouple comprises the following steps:
(1) Magnetron sputtering copper nickel alloy (CuNi) on the surface of the ceramic substrate 44 ) The DPC ceramic film circuit technology is adopted, the substrate is pretreated and cleaned, and a copper-nickel alloy layer is sputtered and combined on the substrate in a vacuum coating mode by utilizing the film professional manufacturing technology;
(2) Processing an etching circuit on the surface of the ceramic substrate, and completing the manufacture of a graphical circuit by adopting the processes of exposure, development, etching and film removal;
(3) Selectively covering solder resist ink on the surface of the ceramic substrate to expose the selected copper-nickel alloy area;
(4) Electroplating copper on the copper-nickel alloy area exposed on the surface of the ceramic substrate;
(5) And (3) carrying out de-inking treatment on the ceramic substrate by using a potassium hydroxide solution to obtain the copper-nickel alloy thin-film thermocouple with a plurality of thermocouple units connected in series.
Example 2
Processing of the human skin simulation thermocouple:
as shown in fig. 2 to 5, the preparation process of the copper-nickel alloy-copper thin film thermocouple comprises the following steps:
(1) Magnetron sputtering copper-nickel alloy (CuNi) on the surface of flexible PI substrate 44 ) The DPC film circuit process is adopted, the substrate is pretreated and cleaned, and a copper-nickel alloy layer is sputtered and combined on the substrate in a vacuum coating mode by utilizing a film professional manufacturing technology;
(2) Processing an etching circuit on the surface of the flexible PI substrate, and finishing the manufacturing of the graphical circuit by adopting the processes of exposure, development, etching and film removal;
(3) Selectively covering solder resist ink on the surface of the flexible PI substrate to expose a selected copper-nickel alloy area;
(4) Electroplating copper on the copper-nickel alloy area exposed on the surface of the flexible PI substrate;
(5) And (3) carrying out de-inking treatment on the flexible PI substrate by using a potassium hydroxide solution to obtain a plurality of copper-nickel alloy thin-film thermocouples with thermocouple units connected in series.
Example 3
Processing of thermocouple for differential thermal analyzer DSC:
as shown in fig. 2 to 5, the preparation process of the copper-nickel alloy-copper thin film thermocouple comprises the following steps:
(1) Magnetron sputtering copper-nickel alloy (CuNi) on the surface of the ceramic substrate 44 ) The DPC ceramic film circuit technology is adopted, the substrate is pretreated and cleaned, and a copper-nickel alloy layer is sputtered and combined on the substrate in a vacuum coating mode by utilizing the film professional manufacturing technology;
(2) Processing an etching circuit on the surface of the ceramic substrate, and completing the manufacture of a graphical circuit by adopting the processes of exposure, development, etching and film removal;
(3) Selectively covering solder resist ink on the surface of the ceramic substrate to expose the selected copper-nickel alloy area;
(4) Electroplating copper on the copper-nickel alloy area exposed on the surface of the ceramic substrate;
(5) And (3) carrying out de-inking treatment on the ceramic substrate by using a potassium hydroxide solution to obtain the copper-nickel alloy thin-film thermocouple with a plurality of thermocouple units connected in series.
(6) And connecting the processed single copper-nickel alloy thin film thermocouple substrates by using a lead to obtain a multilayer laminated thin film thermocouple element.
Example 4
Processing the multilayer superposed thermocouple for detecting the thermal conductivity meter:
as shown in fig. 2 to 5, the preparation process of the copper-nickel alloy-copper thin film thermocouple comprises the following steps:
(1) Magnetron sputtering copper-nickel alloy (CuNi) on the surface of PI substrate 44 ) The DPC film circuit process is adopted, the substrate is pretreated and cleaned, and a copper-nickel alloy layer is sputtered and combined on the substrate in a vacuum coating mode by utilizing a film professional manufacturing technology;
(2) Processing an etching circuit on the surface of the PI substrate, and finishing the manufacture of a graphical circuit by adopting the processes of exposure, development, etching and film removal;
(3) Selectively covering solder resist ink on the surface of the PI base material to expose a selected copper-nickel alloy area;
(4) Electroplating copper on the copper-nickel alloy area exposed on the surface of the PI substrate;
(5) And (3) carrying out de-inking treatment on the PI substrate by using a potassium hydroxide solution to obtain a plurality of copper-nickel alloy thin-film thermocouples with thermocouple units connected in series.
(6) And connecting the processed single copper-nickel alloy thin film thermocouple substrates by using a lead to obtain a multilayer laminated thin film thermocouple element.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single technical solution, and such description is for clarity only, and those skilled in the art should take the description as a whole, and the technical solutions in the embodiments may be combined appropriately to form other embodiments that those skilled in the art can understand. The technical details not described in detail in the present invention can be implemented by any of the prior arts in the field. In particular, all technical features of the invention not described in detail can be achieved by any prior art.
Claims (10)
1. A copper-nickel alloy film thermocouple is characterized in that the copper-nickel alloy film thermocouple is arranged on the surface of an insulating base material and is formed by connecting a plurality of film thermocouple units in series, a bright spot connected to a high-temperature end is copper-nickel alloy, and a bright spot connected to a low-temperature end is copper; the single thin-film thermocouple unit is formed by connecting copper-nickel alloy and copper thin films; the atomic fraction of nickel element in the copper-nickel alloy is 10-90.
2. The cupronickel thin-film thermocouple according to claim 1, characterized in that the atomic fraction of the nickel element in the cupronickel alloy is 44.
3. The cupronickel thin film thermocouple according to claim 1, characterized in that the insulating substrate is at least one of PET, PI, PTFE, ceramics.
4. The cupronickel thin-film thermocouple of claim 1, further comprising a multilayer substrate interconnect structure, said substrate being decorated with a plurality of said thin-film thermocouple cells connected in series.
5. A method for preparing a copper-nickel alloy thin film thermocouple according to any one of claims 1 to 4, comprising the steps of:
(1) Performing magnetron sputtering of copper-nickel alloy on the surface of the substrate;
(2) Processing an etching circuit on the surface of the substrate;
(3) Selectively covering ink on the surface of the substrate to expose the selected copper-nickel alloy area;
(4) Electroplating copper on the copper-nickel alloy area exposed on the surface of the substrate;
(5) And (4) carrying out de-inking treatment on the substrate to obtain the copper-nickel alloy thin-film thermocouple with a plurality of thermocouple units connected in series.
6. The method for preparing a copper-nickel alloy thin film thermocouple according to claim 5, wherein the method comprises the following steps: in the step (1), the copper-nickel alloy is subjected to magnetron sputtering on the surface of the substrate, the DPC thin film circuit process is adopted, the substrate is subjected to pretreatment and cleaning, and the copper-nickel alloy layer is combined on the substrate in a sputtering way by utilizing a special thin film manufacturing technology-vacuum coating mode.
7. The method for preparing a copper-nickel alloy thin film thermocouple according to claim 5, wherein the method comprises the following steps: in the step (1), the atomic fraction of the nickel element in the copper-nickel alloy is 44.
8. The method for preparing a copper-nickel alloy thin film thermocouple according to claim 5, characterized in that: the circuit pattern processing method in the step (2) adopts at least one of photoresist, a dry film and photosensitive ink for processing.
9. The method for preparing a copper-nickel alloy thin film thermocouple according to claim 5, wherein the method comprises the following steps: in the step (5), the de-inking treatment is to remove the ink on the substrate by using a chemical etching method, wherein the used etching solution is alkali liquor, and the alkali liquor is potassium hydroxide.
10. The method for preparing a copper-nickel alloy thin film thermocouple according to claim 5, wherein the method comprises the following steps: the ink in the step (3) is solder resist ink.
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| CA2178175A1 (en) * | 1996-06-04 | 1997-12-05 | Ivo Franolic | Thermal pulse flowmeter sensor |
| JP2003209297A (en) * | 2002-01-15 | 2003-07-25 | Communication Research Laboratory | Woven thermoelectric conversion panel |
| CN101217176A (en) * | 2007-12-27 | 2008-07-09 | 江门金谷电子工业有限公司 | Temperature difference power-generating device |
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| DE102006040576B4 (en) * | 2006-08-30 | 2009-10-08 | Angaris Gmbh | Method for producing a thin-film thermogenerator |
| JP2008108900A (en) * | 2006-10-25 | 2008-05-08 | Toshiba Corp | Thermoelectric conversion module and thermoelectric conversion device |
| JP6291760B2 (en) * | 2012-09-18 | 2018-03-14 | 株式会社リコー | Thermocouple, thermopile, infrared sensor, and method for manufacturing infrared sensor |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CA2178175A1 (en) * | 1996-06-04 | 1997-12-05 | Ivo Franolic | Thermal pulse flowmeter sensor |
| JP2003209297A (en) * | 2002-01-15 | 2003-07-25 | Communication Research Laboratory | Woven thermoelectric conversion panel |
| CN101217176A (en) * | 2007-12-27 | 2008-07-09 | 江门金谷电子工业有限公司 | Temperature difference power-generating device |
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