EP0051826A2 - Procédé de fabrication d'un élément résistif de précision à film épais - Google Patents

Procédé de fabrication d'un élément résistif de précision à film épais Download PDF

Info

Publication number
EP0051826A2
EP0051826A2 EP81109284A EP81109284A EP0051826A2 EP 0051826 A2 EP0051826 A2 EP 0051826A2 EP 81109284 A EP81109284 A EP 81109284A EP 81109284 A EP81109284 A EP 81109284A EP 0051826 A2 EP0051826 A2 EP 0051826A2
Authority
EP
European Patent Office
Prior art keywords
resistance
thick film
paste
alternating voltage
substrate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP81109284A
Other languages
German (de)
English (en)
Other versions
EP0051826A3 (en
EP0051826B1 (fr
Inventor
Yoshio Akimune
Masaaki Uchida
Satoshi Ambe
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nissan Motor Co Ltd
Original Assignee
Nissan Motor Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nissan Motor Co Ltd filed Critical Nissan Motor Co Ltd
Publication of EP0051826A2 publication Critical patent/EP0051826A2/fr
Publication of EP0051826A3 publication Critical patent/EP0051826A3/en
Application granted granted Critical
Publication of EP0051826B1 publication Critical patent/EP0051826B1/fr
Expired legal-status Critical Current

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
    • H01C17/06—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base
    • H01C17/065—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base by thick film techniques, e.g. serigraphy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
    • H01C17/22—Apparatus or processes specially adapted for manufacturing resistors adapted for trimming
    • H01C17/26—Apparatus or processes specially adapted for manufacturing resistors adapted for trimming by converting resistive material
    • H01C17/265—Apparatus or processes specially adapted for manufacturing resistors adapted for trimming by converting resistive material by chemical or thermal treatment, e.g. oxydation, reduction, annealing
    • H01C17/267—Apparatus or processes specially adapted for manufacturing resistors adapted for trimming by converting resistive material by chemical or thermal treatment, e.g. oxydation, reduction, annealing by passage of voltage pulses or electric current

Definitions

  • This invention relates to a method of producing a thick film that serves as a resistive element on an insulating substrate by applying a paste containing a powder of a resistor material onto the surface of the substrate to form a paste layer and then firing the substrate to sinter the resistor material contained in the applied paste, and more particularly to a technique to enhance accuracy of the resistance of the sintered thick film produced by this method.
  • Thick film resistor elements of the above mentioned type are formed largely as basic elements of hydrid integrated circuits, but also they are utilized in some other electric or electronic devices other than integrated circuits.
  • an oxygen sensor element of the solid electrolyte concentration cell type recently used in automobiles includes a thick. film resistor as a heat-generating means for maintaining the sensor element at a desirably elevated temperature.
  • thick film is used in the sense of a film thicker than about 1 ⁇ m, as is customary in the current electronic technology.
  • the thickness of the film may reach tens of microns.
  • a thick film to serve as a resistive element is usually formed by a printing-and-firing method using a paste containing a powder of an electronically conducting resistor material such as a noble metal powder.
  • the first step of this method is to print the paste adjusted to a suitable viscosity onto a major surface of an insulating substrate.
  • a screen-printing method is employed to form a desirably patterned paste layer.
  • the substrate is fired so as to achieve sintering of the resistor material contained in the paste layer.
  • the sintered powder of the resistor material constitutes a thick film which may be microscopically porous but adheres firmly to the surface of the substrate.
  • the resistance of the sintered thick film depends greatly on the thickness of the printed paste layer. Therefore, not only the viscosity of the paste but also the pressure exerted on the squeegee of the screen-printing apparatus 3 and the speed of the movement of the squeegee relative to the screen are minutely adjusted so as to form a paste layer of an appropriate thickness.
  • the thickness control at this stage can be accomplished fairly accurately, but in the case of mass production some dispersion of the thickness values is inevitable.
  • the resistance of the sintered thick film is affected considerably by the firing conditions represented by the firing temperature and the duration of firing, and also by the physical state of the printed and dried layer subject to firing. For these reasons, dispersion of the resistance values of the mass-produced thick film resistor elements is considerably large and sometimes reaches about +20% of the intended value even though the printing process is performed with due control of the thickness. On the other hand, the tolerance of the resistance is rarely larger than ⁇ 5%.
  • a method according to the invention for the production of a thick film resistor element having a predetermined resistance on an insulating substrate has the steps of applying a paste containing a powder of an electronically conducting resistor material dispersed in a liquid vehicle onto a major surface of the substrate to form a paste layer, drying the paste layer and then firing the substrate to achieve sintering of the resistor material contained in the paste layer, and the improvement according to the invention resides in that the above three steps are performed such that a thick film as the product of the firing'step has a provisional resistance lower than the predetermined resistance, and that the method further comprises the step of applying an alternating voltage to the sintered thick film so as to increase the resistance of the thick film up to the predetermined resistance. In this step, the magnitude of the alternating voltage is required to be higher than a maximum voltage to be applied to the thick film resistor element in its practical use.
  • the magnitude of the alternating voltage and the duration of aplication of the alternating voltage would be selectively determined according to the difference between the predetermined resistance and the provisional resistance.
  • the application of an alternating voltage to the sintered thick film causes displacement of microscopical voids among the fine crystal grains of the sintered resistor material as the effect of a phenomenon called electromigration and results in partial breaking of the contacts between the crystal grains. Therefore, the effect of this treatment can be regarded as a decrease in the effective cross-sectional area of the sintered thick film, and a resultant increase in the resistance. As will be understood, the resistance of the sintered thick film under this treatment increases as the duration of the treatment is prolonged and as the magnitude of the alternating voltage is raised.
  • the improvement according to the invention can readily be put into industrial practice without the need of modifying the apparatus and fundamental procedures of the conventional printing-and-firing method and has the effect of enhancing the accuracy of the resistance of the produced thick film resistor elements and greatly increasing the percentage of acceptable products. Therefore, this invention will bring about a considerable reduction of the total production cost and will enable to lower the selling price. Furthermore, this invention is expected to allow automation of the production of thick film resistor elements by a printing-and-firing method.
  • the application of a conducting paste onto a substrate and sintering of the printed and dried paste layer are accomplished by using known techniques. That is, the application of the paste is usually accomplished by a screen-printing method, and the sintering is effected in either air or a non-oxidizing gas atmosphere at a temperature in the range from about 800°C to about 1500°C depending on the kind of the resistor material.
  • the proportion of the provisional resistance R a to the truly desired resistance R s can be selected in a pretty wide range. However, in most cases it is undesirable to make the provisional resistance R a below 50% of the desired resistance R s because the application of an alternating voltage high in magnitude and long in duration enough to increase such a low resistance R a up to the level of R s tends to cause weakening of the mechanical strength of the sintered thick film or the adhesion strength between the thick film and the substrate.
  • a primary factor in determining the proportion of the provisional resistance R a to the desired resistance R s is the width of dispersion of the provisional resistance values R a of the actually obtained sintered thick films in comparison with the tolerance of the resistance R s of the final products.
  • the tolerance of the desired resistance R s is ⁇ 2% (that is, resistance values in the range from 0.98R s to 1.02R s are acceptable) and that actual values of the provisional resistance R a exhibit a dispersion of ⁇ 20%.
  • the provisional resistance R a (as an aimed value or average value) is set at 90% of R , the actual values of R a will disperse in the range from 0.72R s to 1.08RS so that a portion of the sintered thick film become above 1.02R s (upper control limit) in resistance.
  • the magnitude of an alternating voltage used in the method of the invention is usually made to be more than two times as high as a maximum voltage to be applied to the thick film resistor element in its practical use and in most cases does not need to be more than about five times as high as the aforementioned maximum voltage.
  • an alternating voltage of a very low frequency such as about 1/300 Hz to about 1 Hz, and the duration of application of the alternating voltage is usually from several seconds to tens of minutes.
  • the present invention places no particular restriction on the materials or composition of the conducting paste for forming the thick film. That is, conducting pastes conventionally used to produce thick film resistor elements are all useful in the present invention.
  • the paste is a uniform dispersion of a powdered resistor material in a liquid vehicle, which is usually a solution of an organic polymer in an organic solvent.
  • the resistor material may be a noble metal powder such as silver powder, platinum powder or ruthenium powder or a powder of an alloy of noble metals such as Pt-Rh, Ag-Pd, Au-Pt or Au-Pd.
  • such a metal or alloy powder may optionally be admixed with a glass frit powder and/or a metal oxide powder such as Ru0 2 powder, Al 2 0 3 powder or ZrO 2 powder.
  • a metal oxide powder such as Ru0 2 powder, Al 2 0 3 powder or ZrO 2 powder.
  • An example of organic polymers suitable as the binder component of the organic vehicle is a cellulose derivative such as methyl cellulose or ethyl cellulose, and an example of organic solvents suitable to cellulose derivatives is terpineol.
  • the material of the substrate can freely be selected among various ceramic materials. Some examples are alumina, mullite, spinel, silica and forsterite. If desired, it is possible to use a metal substrate having a ceramic coating.
  • a platinum paste was prepared by first dissolving 15 parts by weight of an ethyl cellulose resin in 85 parts by weight of d-terpineol to obtain an organic vehicle and then uniformly dispersing 65 parts by weight of a fine powder of platinum in 35 parts by weight of the organic vehicle.
  • this platinum paste was applied onto a major surface of an alumina substrate 10 by a screen-printing method by using a screen patterned correspondingly to the intended pattern of a thick film to be formed.
  • the printed paste layer was dried at a temperature of 100°C for a period of about 1 hr, and thereafter the substrate 10 with the dried paste layer thereon was fired in air at about 1400°C for 2 hr to thereby achieve sintering of the platinum powder contained in the printed paste layer.
  • the sintered platinum powder constituted a thick film resistor element 12 which adhered firmly to the surface of the substrate 10.
  • Indicated at 14 are a pair of conducting leads, which were arranged prior to the firing process such that the two terminals of the sintered thick film resistor element 12 made intimate contact with the two leads 14, respectively.
  • the thickness of the printed paste layer was controlled such that, when a large number of samples of the thick film 12 were formed by the same procedure and under the same conditions, the average resistance R a of the sintered thick film became 4.8 ohms.
  • a truly desired resistance R s of the thick film resistor element 12 was 6.0 ohms, but it was intended to make the actual resistance R a of the sintered thick films about 80% of the truly desired resistance value R s (6.0 ohms).
  • an alternating voltage was applied by connecting the leads 14 to an alternating voltage supplying circuit 16, which was fundamentally a combination of a DC power supply 18 and a switching device 20 for periodical changeover of the polarity of the output voltage.
  • the circuit 16 was adjusted such that a square wave alternating voltage of the characteristic shown in Fig. 2 was applied to each sample thick film 12. That is, +10 volts and -10 volts were alternated every one minute.
  • the duration of the application of the alternating voltage was varied from Group to Group of the samples and made longer for the samples of smaller resistance values, and more minutely varied for the individual samples of the same Group. The details of the variations are shown in the following Table 1. After the application of the alternating voltage the resistance of each sample was measured.
  • the resistance values measured at this stage are al'so contained in Table 1. Assuming that the tolerance of the desired resistance R is 6.0 ohms ⁇ 2% (i.e. in the range from 5.88 to 6.12 ohms), the samples in Table 1 were evaluated as OK when the resistance after the application of the alternating voltage was within this range but otherwise as NG. It was confirmed that the application of the alternating voltage caused an increase in the resistance of each thick film and that the manner of increase in the resistance was as shown in Fig. 3 for the samples of Groups D, E and F.
  • the above described platinum paste was applied onto the alumina substrate 10 by screen-printing in a rectangular pattern (20 mm x 5 mm), and a cylindrical rod (not illustrated) of alumina having a diameter of 2 mm was vertically placed on the printed paste layer.
  • the substrate was fired in this state at 1400°C for 2 hr to complete the formation of the thick film 12 which adhered to both the substrate 10 and the alumina rod.
  • This thick film was so formed as to have the same thickness as the thick films 12 in the samples subjected to the above described resistance-increasing treatment.
  • the remaining samples were classified into six groups according to the resistance values of the thick films similarly to the Groups A to F in the foregoing test, and the alternating voltage of the characteristic of Fig. 2 was applied to each sample for a period of time different from sample to sample depending on the initial resistance value, as shown in Table 1. After the application of the alternating voltage, every sample was subjected to the above described strength test.
  • the peel strength values measured in this test are also presented in Table 1. From a practical viewpoint, it is required that the peel strength of the thick film after the resistance-increasing treatment be at least 60% of the initial peel strength value, 4.4 kg/mm 2 . In Table 1, therefore, the samples below 2.64 k g/mm 2 in the peel strength are evaluated as NG and the others as OK.
  • the thick film resistor elements produced in this example were intended to be used with the application of a voltage not higher than 3 volts. This means that the magnitude of the voltage used in the resistance-increasing treatment was more than three times as high as a maximum voltage during use of the thick film resistor elements. Therefore, there is little possibility that the resistance of the thick film resistor elements after the treatment will further increase during practical use thereof.
  • the square wave alternating voltage used in this example is merely exemplary. It is also possible to use an alternating voltage of a different waveform such as sine wave or sawtooth wave.
  • a commercially available conducting paste DuPont's No. 9051 paste) containing a silver-palladium powder was applied onto the alumina substrate 10 by the same screen-pringing method as in Example 1.
  • the thickness of the printed paste layer was controlled so as to obtain a thick film having a resistance R of 4.8 ohms.
  • This resistance value R a was 80% of a truly desired resistance R s , 6.0 ohms.
  • the printed paste layer was dried at a temperature of 100°C for a period of 1 hr, and thereafter the substrate with the dried paste layer thereon was fired at about 900°C for 1 hr to thereby achieve sintering of the Ag-Pd powder contained in the printed paste layer.
  • the sintered Ag-Pd powder constituted a thick film resistor element 12 which adhered firmly to the surface of the alumina substrate 10.
  • the leads 14 in Fig. 1 were provided in the same manner as in Example 1.
  • Example 2 To each of these samples, an alternating voltage was applied by using the apparatus 16 described in Example 1.
  • the characteristic of the alternating voltage was as shown in Fig. 2, but in this example the amplitudes of the voltage were +7 volts. That is, +7 volts and -7 volts were alternated every one minute.
  • the duration of the application of the alternating voltage was varied from Group to Group of the samples, and also from sample to sample in the same Group. The details of the variations are shown in Table 2, together with the resistance of each sample measured after the application of the alternating voltage.
  • the criterion for evaluation of the resistance values after the application of the alternating voltage was the same as in Example 1. Fig.
  • Example 4 shows the relationship between the duration of the voltage application in this example and the extent of increase in the resistance of the thick films of the Groups I, J and K samples.
  • the influence of the resistance-increasing treatment on the adhesion strength of the thick film was examined by the peel strength test described in Example 1, and Table 2 contains evaluation of the peel strength after the resistance-increasing treatment on the same criterion as in Example 1.
  • the thick film resistor elements produced in this example were intended to be used with the application of a voltage not higher than 3 volts.

Landscapes

  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Apparatuses And Processes For Manufacturing Resistors (AREA)
  • Parts Printed On Printed Circuit Boards (AREA)
EP19810109284 1980-11-07 1981-10-29 Procédé de fabrication d'un élément résistif de précision à film épais Expired EP0051826B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP15579180A JPS5780708A (en) 1980-11-07 1980-11-07 Method of producing thick film resistor
JP155791/80 1980-11-07

Publications (3)

Publication Number Publication Date
EP0051826A2 true EP0051826A2 (fr) 1982-05-19
EP0051826A3 EP0051826A3 (en) 1983-07-20
EP0051826B1 EP0051826B1 (fr) 1986-02-05

Family

ID=15613504

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19810109284 Expired EP0051826B1 (fr) 1980-11-07 1981-10-29 Procédé de fabrication d'un élément résistif de précision à film épais

Country Status (3)

Country Link
EP (1) EP0051826B1 (fr)
JP (1) JPS5780708A (fr)
DE (1) DE3173741D1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110085383A (zh) * 2019-05-07 2019-08-02 昆山福烨电子有限公司 一种厚膜电阻阻值控制的方法

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61131404A (ja) * 1984-11-29 1986-06-19 ロ−ム株式会社 サ−マルヘツドにおけるパルストリミング法
JPS6370402A (ja) * 1986-09-11 1988-03-30 ロ−ム株式会社 抵抗値トリミング方法
AT519666B1 (de) 2017-11-24 2018-09-15 Blum Gmbh Julius Möbelbeschlag

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3408274A (en) * 1965-07-29 1968-10-29 Du Pont Electrolytic method of adjusting the resistance of palladium glaze resistors
US3603768A (en) * 1969-05-26 1971-09-07 Bunker Ramo Thin-film resistor adjustment
US3676633A (en) * 1970-02-24 1972-07-11 Adm Tronics Electronic trimming of microelectronic resistors
FR2137182A2 (fr) * 1971-05-14 1972-12-29 Commissariat Energie Atomique

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3408274A (en) * 1965-07-29 1968-10-29 Du Pont Electrolytic method of adjusting the resistance of palladium glaze resistors
US3603768A (en) * 1969-05-26 1971-09-07 Bunker Ramo Thin-film resistor adjustment
US3676633A (en) * 1970-02-24 1972-07-11 Adm Tronics Electronic trimming of microelectronic resistors
FR2137182A2 (fr) * 1971-05-14 1972-12-29 Commissariat Energie Atomique

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
21ST ELECTRONIC COMPONENTS CONFERENCE, 10th-12th May 1971, pages 504-511, Washington D.C. (USA); *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110085383A (zh) * 2019-05-07 2019-08-02 昆山福烨电子有限公司 一种厚膜电阻阻值控制的方法

Also Published As

Publication number Publication date
JPS5780708A (en) 1982-05-20
DE3173741D1 (en) 1986-03-20
EP0051826A3 (en) 1983-07-20
EP0051826B1 (fr) 1986-02-05

Similar Documents

Publication Publication Date Title
US6411012B2 (en) Multilayer piezoelectric element and method of producing the same
US3374110A (en) Conductive element, composition and method
US5861558A (en) Strain gauge and method of manufacture
US4409135A (en) Paste containing electrically conducting powder to form conducting solid filler in cavity in ceramic substrate
EP0008175A1 (fr) Procédé de fabrication d'une couche frittée, mince et dense
US5189284A (en) Resistor, process for producing the same, and thermal head using the same
EP0051826B1 (fr) Procédé de fabrication d'un élément résistif de précision à film épais
DE102009026439A1 (de) Sensorelement und Verfahren zur Herstellung eines solchen
Dziedzic et al. Advanced electrical and stability characterization of untrimmed and variously trimmed thick-film and LTCC resistors
Coleman et al. Silver migration in thick film conductors and chip attachment resins
Prudenziati et al. Excess noise and refiring processes in thick-film resistors
JPH08304200A (ja) 感歪み抵抗体ペーストおよびこれを用いた力学量センサ
US5463367A (en) Method for forming thick film resistors and compositions therefor
EP0341708B1 (fr) Résistance en couche mince et procédé de fabrication
Reissing An overview of today's thick-film technology
JPH0376201A (ja) 層状厚膜抵抗器及びその製造方法
JPS58198754A (ja) ガスセンサ素子用ヒ−タ付基板の製造方法
JPH01304702A (ja) 抵抗体の製造方法及びサーマルヘッドの製造方法
JP2817151B2 (ja) 抵抗体の製造方法及びサーマルヘッドの製造方法
JP2759995B2 (ja) 抵抗体の製造方法及びその抵抗体を用いたサーマルヘッドの製造方法
JP3673032B2 (ja) セラミック回路基板及びその製造方法
JPH113802A (ja) 低温焼成用抵抗ペースト
JPH05126616A (ja) 液面レベル計
Wassmer et al. Inkjet Printing of Thick-Film Resistors
CA2018113A1 (fr) Resistance a film epais multicouches et methode de fabrication desdites resistances

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Designated state(s): DE FR GB

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

RHK1 Main classification (correction)

Ipc: H01C 17/26

AK Designated contracting states

Designated state(s): DE FR GB

17P Request for examination filed

Effective date: 19830616

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: NISSAN MOTOR CO., LTD.

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Designated state(s): DE FR GB

REF Corresponds to:

Ref document number: 3173741

Country of ref document: DE

Date of ref document: 19860320

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
GBPC Gb: european patent ceased through non-payment of renewal fee
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19880630

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19880701

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19881118