EP0810612B1 - Indiumhaltiger, oxidkeramischer Thermistor - Google Patents

Indiumhaltiger, oxidkeramischer Thermistor Download PDF

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Publication number
EP0810612B1
EP0810612B1 EP97201533A EP97201533A EP0810612B1 EP 0810612 B1 EP0810612 B1 EP 0810612B1 EP 97201533 A EP97201533 A EP 97201533A EP 97201533 A EP97201533 A EP 97201533A EP 0810612 B1 EP0810612 B1 EP 0810612B1
Authority
EP
European Patent Office
Prior art keywords
thermistor
spinel
oxide
composition
indium
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.)
Expired - Lifetime
Application number
EP97201533A
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German (de)
English (en)
French (fr)
Other versions
EP0810612A1 (de
Inventor
Wilhelm Albert Dr. Groen
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.)
Philips Intellectual Property and Standards GmbH
Koninklijke Philips NV
Original Assignee
Philips Corporate Intellectual Property GmbH
Philips Patentverwaltung GmbH
Koninklijke Philips Electronics NV
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 Philips Corporate Intellectual Property GmbH, Philips Patentverwaltung GmbH, Koninklijke Philips Electronics NV filed Critical Philips Corporate Intellectual Property GmbH
Publication of EP0810612A1 publication Critical patent/EP0810612A1/de
Application granted granted Critical
Publication of EP0810612B1 publication Critical patent/EP0810612B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C7/00—Non-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
    • H01C7/04—Non-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
    • H01C7/042—Non-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
    • H01C7/043—Oxides or oxidic compounds

Definitions

  • the invention relates to a thermistor with a semiconductor ceramic with an indium-containing manganese-nickel-oxide spinel.
  • Thermistors also called NTC resistors, have a negative temperature coefficient (NTC), their resistivity decreases with temperature approximately exponentially.
  • NTC negative temperature coefficient
  • Semiconducting oxide ceramics are used. Ceramic thermistors are widely used as temperature sensors, e.g. B. in the food and plastics industries, in automotive electronics, in portable measuring instruments and in medical technology, also as a clinical thermometer. Part of the applications concerns the temperature compensation of coils, the working point stabilization of Transistors and the overtemperature protection of electronic devices. Beneficial Applications also arise in low-temperature measuring technology, as Radiation receivers in pyrometers and as transmitters in flow anemometers.
  • oxide spinels An important group of ceramic materials for the manufacture of thermistors are the oxide spinels. These are ionic crystals with the composition AB 2 O 4 , the structure of which is determined by the cubic closest packing of the large negatively charged oxygen ions O 2- . The larger cations A occupy octahedral gaps of the anion lattice, the smaller cations B the tetrahedral gaps of the anion lattice.
  • Today's thermistor components are based almost exclusively on mixed crystals with a spinel structure, which are generally composed of 2 to 4 cations from the group manganese, nickel, cobalt, iron, copper and titanium.
  • One problem, however, is the thermal stability of these connections. In order to obtain uniform spinel phases, precise process control is necessary even in the manufacturing process. In addition, the working temperatures must not exceed certain upper limit values.
  • NTC resistors with the general formula Zn z Fe xz III Ni Mn 2-xz III Mn z IV O 4 with 0 ⁇ z ⁇ x. These oxide spinels form a uniform spinel phase, they do not fall into separate oxide phases during production and can therefore be produced with a reproducible setting of the thermistor parameters.
  • the object is achieved by a thermistor with a semiconductor ceramic with an indium-containing manganese-nickel-oxide spinel.
  • a thermistor with a semiconductor ceramic with an oxide spinel that the Containing elements of manganese, nickel and indium is thermodynamically very stable because Indium only occurs in one oxidation state (+3) and therefore not with oxygen the atmosphere reacts. It continues to be characterized by high values for the specific resistance and the B value.
  • the oxide spinel has the composition Mn 2.33-x In x Ni 0.67 O 4 with 0.05 x x 0,7 0.75.
  • Spinels with this composition are particularly stable at high working temperatures because their crystal structure is monomorphic, ie they do not change at higher temperatures.
  • the spinel has the composition Mn 2.33-x In x Ni 0.67 O 4 with 0.5 ⁇ x ⁇ 0.66.
  • a thermistor with such a composition has a surprisingly high thermal stability of the resistance value in the long-term test.
  • Fig. 1 Specific resistance and B value as a function of the indium content x in Mn 2.33-x In x Ni 0.67 O 4 .
  • the thermistor according to the invention contains a semiconductor ceramic with an oxide spinel, which contains the elements manganese, nickel and indium, in particular those of the composition Mn 2.33-x In x Ni 0.67 O 4 with 0.05 x x 0,7 0.75 . Due to the low electron affinity and the high ionization potential of the indium (+3), this oxide spinel is redox-stable and does not change through interaction with the atmosphere at elevated temperatures.
  • the composition of the spinel is preferably chosen so that it is close to the phase transition from the cubic to the tetragonal spinel structure and the composition Mn 2.33-x In x Ni 0.67 O 4 with 0.05 ⁇ x ⁇ 0 , 75 has. Surprisingly, it has been found that these compositions show minimal aging.
  • the thermistor is manufactured according to the usual ceramic manufacturing methods, depending on the desired tolerances and the field of application numerous variants are possible.
  • the starting compounds can be from Oxides, hydroxides, carbonates, oxalates and the like. use. These are according to weighed the desired composition, wet milled, dried and granulated. Then you can the oxide mixture at 900 ° C to 1000 ° C. calcine to achieve pre-compaction and chemical homogenization. The calcined mixture is ground again and with a binder composition suspended. This is followed by the design.
  • the powder suspension can be cast into foils or for circuits using thick film technology Substrate to be screen printed. The suspension can also be processed into granules are, from which any shape can then be pressed. Subsequently first the binder burnout and then the final sintering takes place the spinel phase is formed. In a further process step, the Contacts applied.
  • Single-phase oxide spinels are formed, which contain the elements manganese, nickel and Contain indium. This is confirmed by X-ray examinations.
  • the corresponding starting oxides are mixed in a stoichiometric mixing ratio and ground with zircon grinding balls for 16 hours.
  • the premixed powder is granulated with a conventional binder preparation. Tablets with a diameter of 6 mm and a thickness of 1 mm are pressed from the granules. These tablets are sintered in the air for six hours at 1250 ° C. X-ray diffraction images show that the semiconductor ceramic obtained in this way is a single-phase material with a spinel structure.
  • the relative density of the mixed crystal oxides is greater than 97% of the theoretical density.
  • Fig. 1 shows that the main thermistor parameters, ie the specific resistance (R 25 ) and the B value increase with increasing indium content.
  • the aging tests were carried out at 150 ° C for 1800 h.
  • the thermistor parameters R 25 and the thermal constant B were measured at intervals. The tests showed that the aging is practically complete after 150 h.
  • the experiments further showed that the relative change in the resistance R / R 0 with time near the phase boundary between the cubic and tetragonal phase boundary has a minimum.

Landscapes

  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Thermistors And Varistors (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
EP97201533A 1996-06-01 1997-05-22 Indiumhaltiger, oxidkeramischer Thermistor Expired - Lifetime EP0810612B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19622112A DE19622112A1 (de) 1996-06-01 1996-06-01 Indiumhaltiger, oxidkeramischer Thermistor
DE19622112 1996-06-01

Publications (2)

Publication Number Publication Date
EP0810612A1 EP0810612A1 (de) 1997-12-03
EP0810612B1 true EP0810612B1 (de) 1999-09-01

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP97201533A Expired - Lifetime EP0810612B1 (de) 1996-06-01 1997-05-22 Indiumhaltiger, oxidkeramischer Thermistor

Country Status (5)

Country Link
US (1) US5976421A (ja)
EP (1) EP0810612B1 (ja)
JP (1) JPH1092609A (ja)
DE (2) DE19622112A1 (ja)
TW (1) TW406061B (ja)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ATE434823T1 (de) * 2000-04-25 2009-07-15 Epcos Ag Elektrisches bauelement, verfahren zu dessen herstellung und dessen verwendung
JP3711857B2 (ja) * 2000-10-11 2005-11-02 株式会社村田製作所 負の抵抗温度特性を有する半導体磁器組成物及び負特性サーミスタ
JP4601300B2 (ja) * 2004-01-28 2010-12-22 京セラ株式会社 半導電性セラミックス及びこれを用いた画像形成装置
DE102008009817A1 (de) * 2008-02-19 2009-08-27 Epcos Ag Verbundwerkstoff zur Temperaturmessung, Temperatursensor aufweisend den Verbundwerkstoff und Verfahren zur Herstellung des Verbundwerkstoffs und des Temperatursensors
JP6975333B2 (ja) 2018-07-13 2021-12-01 株式会社日立製作所 永久磁石同期機制御装置、電気車および永久磁石同期機の磁極極性判別方法
EP3901115A1 (en) 2020-04-24 2021-10-27 Nederlandse Organisatie voor toegepast- natuurwetenschappelijk Onderzoek TNO A printable ntc ink composition and method of manufacturing thereof

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS54111700A (en) * 1978-02-22 1979-09-01 Hitachi Ltd Thermistor composition
US5246628A (en) * 1990-08-16 1993-09-21 Korea Institute Of Science & Technology Metal oxide group thermistor material
DE4213629C1 (de) * 1992-04-24 1994-02-17 Siemens Matsushita Components Sinterkeramik für hochstabile Thermistoren und Verfahren zu ihrer Herstellung
EP0637292A1 (de) * 1992-04-24 1995-02-08 SIEMENS MATSUSHITA COMPONENTS GmbH & CO. KG Sinterkeramik für hochstabile thermistoren und verfahren zu ihrer herstellung
EP0641144A1 (en) * 1993-08-09 1995-03-01 Matsushita Electric Industrial Co., Ltd. Metal oxide film resistor and method for producing the same
DE4420657A1 (de) * 1994-06-14 1995-12-21 Siemens Matsushita Components Sinterkeramik für hochstabile Thermistoren und Verfahren zu ihrer Herstellung
US5830268A (en) * 1995-06-07 1998-11-03 Thermometrics, Inc. Methods of growing nickel-manganese oxide single crystals

Also Published As

Publication number Publication date
EP0810612A1 (de) 1997-12-03
DE59700382D1 (de) 1999-10-07
US5976421A (en) 1999-11-02
JPH1092609A (ja) 1998-04-10
DE19622112A1 (de) 1997-12-04
TW406061B (en) 2000-09-21

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