DE3522427A1 - Titanium oxynitride layer for use in sensors - Google Patents
Titanium oxynitride layer for use in sensorsInfo
- Publication number
- DE3522427A1 DE3522427A1 DE19853522427 DE3522427A DE3522427A1 DE 3522427 A1 DE3522427 A1 DE 3522427A1 DE 19853522427 DE19853522427 DE 19853522427 DE 3522427 A DE3522427 A DE 3522427A DE 3522427 A1 DE3522427 A1 DE 3522427A1
- Authority
- DE
- Germany
- Prior art keywords
- layer according
- oxynitride layer
- titanium oxynitride
- titanium
- approx
- 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
Links
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 239000010936 titanium Substances 0.000 title claims abstract description 76
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 76
- 239000000463 material Substances 0.000 claims abstract description 25
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000001301 oxygen Substances 0.000 claims abstract description 19
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- 238000009529 body temperature measurement Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 239000012298 atmosphere Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 19
- 230000008569 process Effects 0.000 claims description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 13
- 238000002161 passivation Methods 0.000 claims description 12
- 239000004065 semiconductor Substances 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 229910010282 TiON Inorganic materials 0.000 claims description 5
- 238000005516 engineering process Methods 0.000 claims description 5
- 230000007774 longterm Effects 0.000 claims description 5
- 239000012495 reaction gas Substances 0.000 claims description 5
- 238000004544 sputter deposition Methods 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 238000005496 tempering Methods 0.000 claims description 4
- 229910010303 TiOxNy Inorganic materials 0.000 claims description 3
- 239000004020 conductor Substances 0.000 claims description 3
- 238000007733 ion plating Methods 0.000 claims description 3
- 238000005259 measurement Methods 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 229910005544 NiAg Inorganic materials 0.000 claims description 2
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 2
- 229910000831 Steel Inorganic materials 0.000 claims description 2
- 238000009530 blood pressure measurement Methods 0.000 claims description 2
- 239000012876 carrier material Substances 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- 238000010894 electron beam technology Methods 0.000 claims description 2
- 230000002401 inhibitory effect Effects 0.000 claims description 2
- 238000004518 low pressure chemical vapour deposition Methods 0.000 claims description 2
- 238000001020 plasma etching Methods 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 239000010959 steel Substances 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims 5
- 230000008020 evaporation Effects 0.000 claims 2
- 238000001704 evaporation Methods 0.000 claims 2
- 238000001465 metallisation Methods 0.000 claims 2
- 239000010409 thin film Substances 0.000 claims 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims 1
- 229910003074 TiCl4 Inorganic materials 0.000 claims 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims 1
- 239000012299 nitrogen atmosphere Substances 0.000 claims 1
- 230000001590 oxidative effect Effects 0.000 claims 1
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims 1
- 238000011417 postcuring Methods 0.000 claims 1
- 238000000992 sputter etching Methods 0.000 claims 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims 1
- 238000007704 wet chemistry method Methods 0.000 claims 1
- 230000008859 change Effects 0.000 abstract description 5
- 230000008021 deposition Effects 0.000 abstract description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005546 reactive sputtering Methods 0.000 description 2
- 229910017083 AlN Inorganic materials 0.000 description 1
- 229910001006 Constantan Inorganic materials 0.000 description 1
- 229910019974 CrSi Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 229910010066 TiC14 Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229940110728 nitrogen / oxygen Drugs 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 229910001258 titanium gold Inorganic materials 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 238000003631 wet chemical etching Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0676—Oxynitrides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/308—Oxynitrides
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01L—MEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
- G01L1/00—Measuring force or stress, in general
- G01L1/20—Measuring force or stress, in general by measuring variations in ohmic resistance of solid materials or of electrically-conductive fluids; by making use of electrokinetic cells, i.e. liquid-containing cells wherein an electrical potential is produced or varied upon the application of stress
- G01L1/22—Measuring force or stress, in general by measuring variations in ohmic resistance of solid materials or of electrically-conductive fluids; by making use of electrokinetic cells, i.e. liquid-containing cells wherein an electrical potential is produced or varied upon the application of stress using resistance strain gauges
- G01L1/2287—Measuring force or stress, in general by measuring variations in ohmic resistance of solid materials or of electrically-conductive fluids; by making use of electrokinetic cells, i.e. liquid-containing cells wherein an electrical potential is produced or varied upon the application of stress using resistance strain gauges constructional details of the strain gauges
-
- 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
- H01C7/02—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 positive temperature coefficient
- H01C7/022—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 positive temperature coefficient mainly consisting of non-metallic substances
-
- 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
-
- 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
- H01C7/06—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 including means to minimise changes in resistance with changes in temperature
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electromagnetism (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Ceramic Engineering (AREA)
- Physical Vapour Deposition (AREA)
Abstract
Description
Die Erfindung betrifft ein Material, das sich aus den Elementen Titan,The invention relates to a material consisting of the elements titanium,
Sauerstoff und Stickstoff (TiOxNy) zusammensetzt und je nach deren relativen Volumenanteilen unterschiedliche Eigenschaften aufweist, die das Material vorteilhaft für verschiedene Sensoranwendungen verwendbar macht.Oxygen and nitrogen (TiOxNy) composed and depending on them relative volume proportions has different properties that the material Makes it useful for various sensor applications.
Titannitrid (TiN) ist als tribologische Schicht hoher Härte z.B. für Werkzeugbeschichtungen (spanabhebende Werkzeuge) bekannt (z.B. 51,22). Weiterhin läßt es sich wegen der kleinen Diffusionskoeffizienten,die viele Elemente in diesem Material aufweisen (z.B. Pt, Au, B, P),auch als hochtemperaturstabile Diffusionsbarriere z.B. in der Halbleitertechnik zur gezielten Einstellung von Dotierungen und für Metall-Halbleiterkontakte verwenden ~3-6 Zudem weist TiN einen kleinen spezifischen Widerstand auf (2050@- cm) und hat einen Temperaturkoeffizienten des elektrischen Widerstandes (TCR) von ca. 0,3X/K, der dem von Metallen entspricht.Titanium nitride (TiN) is used as a tribological layer of high hardness, e.g. for Tool coatings (cutting tools) known (e.g. 51,22). Farther it can be because of the small diffusion coefficient that many elements in this Have material (e.g. Pt, Au, B, P), also as a high-temperature stable diffusion barrier e.g. in semiconductor technology for the targeted adjustment of doping and for Use metal-semiconductor contacts ~ 3-6 In addition, TiN has a small specific Resistance to (2050 @ - cm) and has a temperature coefficient of electrical Resistance (TCR) of approx. 0.3X / K, which corresponds to that of metals.
Die vorliegende Erfindung nutzt den Effckt, daß durch gezielte Substitution eines Teiles der Stickstoffatome im TiN durch Sauerstoff entsprechend TiOxNy mit 1-<+ ys2 sich die elektrischen Eigenschaften des Materials definiert verändern lassen. Diese Veränderungen betreffen folgende Eigenschaften: 1. Der spezifische Widerstand des Materials erhöht sich mit zunehmenden Sauerstoffanteil (von ca. 20@@ cm cm (TiN) auf klicm bei TiO2) -. Der Temperaturkoeffizient des Widerstandes (TCR) wechselt mit 7jnehmendem Sauerstoffanteil von positiven ( + 0,3.%/K) auf negative Werte (>-1%/K) Damit lassen sich gegenüber dem Stand der Technik, wie er durch eine Vielzahl von Materialien vertreten wird wie z.B. Pt für die Temperaturmessung mit positiven TCR, Konstantan oder CrSi für temperaturabhängige Widerstände und Dehnungsmeßstreifen, halbleitende Materialien wie Metalloxide oder Silizium und Germanium mit negativen TCR für Anwendungen für Temperaturregelungen, mit einem Material alle diese Eigenschaften durch geringfügige Variation der Abscheideparameter erreichen. Gleichzeitig weist dieses Material den Vorteil auf, daß es für verschiedene Anwendungen bis zu höheren Temperaturen (>2000C) beständig ist, was beispielsweise für Dehnungsmeßstreifen z.B. für Drucksensoren technisch besonders interessant ist. Damit öffnet sich ein weiterer Anwendungsbereich z.B. in der Druckmessung bei der Hydraulik und in der Motorenüberwachung.The present invention utilizes the effect that through targeted substitution a part of the nitrogen atoms in TiN by oxygen corresponding to TiOxNy with 1 - <+ ys2 the electrical properties of the material change in a defined manner permit. These changes affect the following properties: 1. The specific one Resistance of the material increases with increasing oxygen content (from approx. 20 @@ cm cm (TiN) on click for TiO2) -. The temperature coefficient of resistance (TCR) changes with increasing oxygen content from positive (+ 0.3% / K) to negative Values (> -1% / K) This means that compared to the state of the art, as represented by a variety of materials such as Pt for temperature measurement with positive TCR, constantan or CrSi for temperature-dependent resistances and Strain gauges, semiconducting materials such as metal oxides or silicon and Germanium with negative TCR for temperature control applications, with a Material all these properties by slightly varying the deposition parameters reach. At the same time, this material has the advantage that it is suitable for various Applications up to higher temperatures (> 2000C) is resistant, which is for example for strain gauges, e.g. for pressure sensors, is of particular technical interest. This opens up a further area of application, e.g. in pressure measurement in the Hydraulics and in engine monitoring.
Entgegen den in der Literatur angegebenen Deutungen dieser Effekte, die dies als Veränderung der Titan-Stickstoff-Stöchiometrie beschreiben tz.B. g 7,80) ist dafür allein der eingebaute Sauerstoff verantwortlich. In den genannten Zitaten wurde er möglicherweise prozeßbedingt eingebaut, ohne erkannt zu werden.Contrary to the interpretations of these effects given in the literature, who describe this as a change in the titanium-nitrogen stoichiometry tz.B. G 7.80) is solely responsible for the built-in oxygen. In the mentioned Quotations may have been incorporated into the process without being recognized.
Zur Verdeutlichung zeigt Bild 1 den Verlauf vom spezifischen Widerstand und Temperaturkoeffizient als Funktion der Stickstoffkonzentration im Reaktionsgas, wenn als Darstellungsverfahren reaktives Sputtern vom Titantarget eingesetzt wird.For clarification, Figure 1 shows the specific resistance curve and temperature coefficient as a function of the nitrogen concentration in the reaction gas, when reactive sputtering of the titanium target is used as the display method.
Vergleichbare Verläufe erhält man, wenn die Stöchiometrie in anderen Darstellungsverfahren wie reaktivem Dampfen, Ionenplattieren oder in CVD-Verfahren verändert wird.Comparable gradients are obtained when the stoichiometry in others Representation processes such as reactive vaporization, ion plating or in CVD processes is changed.
Fügt man bei konstanter Stickstoff-Konzentration dem Reaktionsgas unterschiedliche Mengen Sauerstoff hinzu (besonders interessant ist der Bereich um 10% 02), so erhält man spezifische Widerstände und Temperaturkoeffizienten, wie sie in Bild 2 dargestellt sind. Bemerkenswert ist der Nulldurchgang des Temperaturkoeffizienten, der es erlaubt, Widerstände mit positivem (PTC), negativen (NTC) als auch verschwindendem TCR zu erzeugen. Zudem läßt sich der spezifische Widerstand selbst um Größenordnungen verändern.It is added to the reaction gas with a constant nitrogen concentration different amounts of oxygen are added (the range is particularly interesting by 10% 02), one obtains specific resistances and temperature coefficients such as they are shown in Figure 2. The zero crossing of the temperature coefficient is remarkable, which allows resistances with positive (PTC), negative (NTC) and vanishing Generate TCR. In addition, the specific resistance itself can be increased by orders of magnitude change.
Für die Anwendung für Sensoren sind folgende weitere physikalische Eigenschaften von Bedeutung - Die Langzeitstabilität der elektrischen Daten auch bei hohen Temperaturen; TiON-Schichten sind bis ca. 3000C an Luft, bis 6000C im Vakuum langzeitstabil, d.h. die physikalischen Eigenschaften bleiben konstant. Für Temperaturen oberhalb 300°C kann durch eine sauerstoffhemmende oder sauerstoffundurchlässige Passivierung eine Oxidation des TiON an Luft verhindert werden. Damit ist auch an Normalatmosphäre ein Einsatz bei hohen Temperaturen möglich. Vorteilhaft ist es hier z.B. Si3N4, SiO2, Al203 oder AlN als Passivierung zu verwenden. Vorteilhaft kann es auch sein, TiON-Schichten beiderseitig in solche Passivierungsschichten einzubeten, um eine Verunreinigung der Schichten zu verhindern.The following additional physical ones are used for sensors Properties of importance - The long-term stability of the electrical data too at high temperatures; TiON layers are up to approx. 3000C in air, up to 6000C in Long-term vacuum stability, i.e. the physical properties remain constant. For Temperatures above 300 ° C can be caused by an oxygen-inhibiting or oxygen-impermeable Passivation prevents oxidation of the TiON in air. This is also on Normal atmosphere, use at high temperatures is possible. It is beneficial here e.g. Si3N4, SiO2, Al203 or AlN to be used as passivation. Advantageous it can also be TiON layers on both sides in such passivation layers to prevent contamination of the layers.
- der Dehnungsfaktor (K-Faktor) für die Anwendung des Materials als Dehnungsmeßstreifen z.B.C9~7 Bei reinem TiN läßt sich ein Dehnungsfaktor (K-Faktor) von ca. 8 gegenüber dem Geometriefaktor 2 der meisten Metalle erreichen. Durch Zugabe von Sauerstoff verringert er sich,um bei einen TCR von -50ppm1TCR L + 50ppm, wie er reproduzierbar erzielbar ist, gemäß Bild 3 ca. 4 zu erreichen. Ein TCR von etwa Null wird für Kraft- und Druckaufnehmer angestrebt, um das Meßsignal durch den Temperaturgang des Widerstandes nicht zu verfälschen.- the expansion factor (K-factor) for the application of the material as Strain gauges e.g. C9 ~ 7 With pure TiN, a strain factor (K-factor) of about 8 compared to the geometry factor 2 of most metals. By adding of oxygen it decreases to at a TCR of -50ppm1TCR L + 50ppm, like it can be reproducibly achieved, according to Fig. 3 it can be reached approx. 4. A TCR of around The aim for force and pressure transducers is zero, in order to pass the measurement signal through the temperature curve of resistance not to falsify.
- der Temperaturkoeffizient des Dehnungsfaktors (TCK) liegt im technisch interessanten Bereich und kann eingestellt werden.- The temperature coefficient of the expansion factor (TCK) is in the technical interesting area and can be adjusted.
Er liegt bei einem TCR von ca.+ 50ppm bei ca -300 bis -500ppm/K und kompensiert damit den Temperaturgang des Elastizitätsmoduls üblicher DMS-Trägermaterialien (z.B. Stahl, OuBe-300ppm/K). Durch Tempern läßt sich der TCK optimieren. With a TCR of approx. + 50ppm, it is approx. -300 to -500ppm / K and thus compensates for the temperature change of the elasticity module of conventional strain gage carrier materials (e.g. steel, OuBe-300ppm / K). The TCK can be optimized by tempering.
- der thermische Ausdehnungskoeffizient Yth bleibt dem von Metallen sehr nahe, was besonders für Hochtemperaturanwendungen der TiO N -Schichten xy auf Metallträgern bedeutungsvoll ist.- the coefficient of thermal expansion Yth remains that of metals very close, which is especially true for high temperature applications of the TiO N layers xy Metal beams is meaningful.
Wegen seiner guten chemischen und thermischen Beständigkeit ist Ti0 Ny auch in ungünstiger Umgebung geeignet. Als Anwendung lassen sich folgende Bereiche angeben: t. Druck- und Kraftmessung Dehnungsmeßstreifen aus TiO N mit einem K-Faktor im Bereich von 2-8 bei /TCR/# 50ppm mit K-Faktor um 4 und TCK~-300ppm auch oberhalb 200° C 2. Für Temperaturmessung TCR positiv oder negativ je nach gewünschter Höhe und Verlauf mit paralleler Einstellung des spezifischen Widerstandes 3. Hochtemperaturfeste und mechanisch und chemisch widerstandfähige Leiterbahnen für Dünn- und Dickschichtschaltungen 4. Heizwendel für Dünn- und Dickschichtschaltungen z.B. für chemische Sensoren.Because of its good chemical and thermal resistance, Ti0 Ny also suitable in unfavorable surroundings. The following areas can be used specify: t. Pressure and force measurement, strain gauges made of TiO N with a K factor in the range of 2-8 at / TCR / # 50ppm with K-factor around 4 and TCK ~ -300ppm also above 200 ° C 2. For temperature measurement TCR positive or negative depending on the desired height and curve with parallel adjustment of the specific resistance 3. High temperature resistant and mechanically and chemically resistant conductor tracks for thin and thick-film circuits 4. Heating coil for thin and thick film circuits, e.g. for chemical sensors.
Um die o.g. spezifischen Eigenschaften des TiO zu erreichen, muß das xy Darstellungsverfahren folgende Kriterien erfüllen: 1. Reduzierung des Sauerstoffpartialdruckes in der Apparatur inclusive der oasführenden Systeme vor Beginn des Prozesses, vorteilhaft auch unter 10-2 Pa.In order to achieve the above-mentioned specific properties of TiO, it must xy display methods meet the following criteria: 1. Reduction of the oxygen partial pressure in the apparatus including the oasleitenden systems before the start of the process, advantageous also below 10-2 Pa.
2. Definierte Zugabe der den Stickstoff liefernden Komponente im Reaktionsgas auf eine relative Partialdruckabweichung von ru, 5% 3. Definierte Zugabe des Sauerstoffs im Reaktionsgas auf ca. 0,2% des Stickstoffpartialdruckes 4. Verwendung hochreiner Reaktionsgase, vorteilhaft 5-Neuner Folgende Herstellungsverfahren für TiOXNy sind vorteilhaft 1. Reaktives Sputtern Dem^Sputtergas, vorzugsweise Argon (Druck z.B. 0,2 Pa) wird Stickstoff vorteilhaft mit einen Partialdruck vonca.4-10-²Pa zugegeben. Zur Einstellung eines TCR von etwa Null wirdca.4.10-³ Pa C2 hinzugefügt. Als Targetmaterial wird vorteilhaft Titan verwendet, die Sputterrate (DC oder HF) beträgt ca.1,8 µm 1h. Das Substrat wird vorteilhaft auf ca. 300°C erwärmt 2. Reaktives Dampfen und Ionenplattieren Titan wird vorteilhaft mit einer Elektronenstrahlkanone verdampft in einer Atmosphäre von N2 und 02 von ca. 10-2 bzw. 103 Pa.2. Defined addition of the nitrogen-supplying component in the reaction gas to a relative partial pressure deviation of ru, 5% 3. Defined addition of oxygen in the reaction gas to approx. 0.2% of the nitrogen partial pressure 4. Use of high-purity Reaction gases, advantageously 5-nines The following manufacturing processes for TiOXNy are Advantageous 1. Reactive sputtering The sputtering gas, preferably argon (pressure e.g. 0.2 Pa) nitrogen is advantageously added at a partial pressure of about 4-10-2 Pa. Approximately 4.10-3 Pa C2 is added to set a TCR of approximately zero. As target material Titanium is advantageously used, the sputtering rate (DC or HF) is around 1.8 µm 1h. The substrate is advantageously heated to approx. 300 ° C 2. Reactive Steaming and ion plating titanium is beneficial with an electron beam gun evaporates in an atmosphere of N2 and 02 of approx. 10-2 and 103 Pa, respectively.
3. Pyrolytisches Abscheiden (CVD) Wegen der hohen Anforderungen an die definierte Sauerstoffzugabe sind Niederdruck- und Plasma-CVD-Verfahren zu bevorzugen. Bei genügender Spülung, vorteilhaft mit H2, des Reaktionsraumes kann aber auch bei Normaldruck gearbeitet werden. Vorteilhaft sind Abscheidetemperaturen von 500 bis 9000C mit Reaktionsgasen von NH3 (Stickstoffquelle) oder N2 und 02 sowie z.B. TiC14 als Titanquelle.3. Pyrolytic deposition (CVD) Because of the high demands on the defined addition of oxygen, low-pressure and plasma CVD processes are preferred. With sufficient rinsing, advantageously with H2, the reaction space can also be used with Normal pressure can be worked. Deposition temperatures of 500 to are advantageous 9000C with reaction gases of NH3 (nitrogen source) or N2 and 02 as well as e.g. TiC14 as a source of titanium.
Das Verhältnis der Partialdrücke von Stickstoff/Sauerstoff ist entsprechend zu wählen. Für den beabsichtigten Einsatz sind optimale Schichtdicken von 0,1 bis Spm vorteilhaft. The ratio of the partial pressures of nitrogen / oxygen is corresponding to choose. For the intended use, optimal layer thicknesses of 0.1 to Spm beneficial.
Zur Strukturierung der Schichten eignen sich übliche naß- und trockenchemische Verfahren wie: Naßchemisches Ätzen, vorteilhaft z.B. mit H2SO4, H202 und H20, Plasma Ätzen, vorteilhaft mit Freon, Rücksputtern und Tonenätzen, vorteilhaft mit Argon. Customary wet and dry chemical methods are suitable for structuring the layers Processes such as: wet chemical etching, advantageous e.g. with H2SO4, H202 and H20, plasma Etching, advantageously with Freon, backsputtering and clay etching, advantageously with argon.
Als Maskierung werden z.B. in der Halbleitertechnik übliche Verfahren verwendet.The usual methods of masking are used, for example, in semiconductor technology used.
Kontaktiert werden kann TiON mit beliebiger Zusammensetzung vorteilhaft mit üblichen Metallkontakten, wie sie auch in der Halbleitertechnik üblich sind wie TiAu, TiPtAu, CrPdAg, CrAu, TiAg, Trag, NiAu, NiAg.TiON with any composition can advantageously be contacted with conventional metal contacts, as they are also common in semiconductor technology like TiAu, TiPtAu, CrPdAg, CrAu, TiAg, Trag, NiAu, NiAg.
Für Temperaturen bis 5000C ist Platin allein, auch bei atmosphärischer Umgebung, im Vakuum ist Ni bis über 6000C vorteilhaft. Zur Kontaktierung für hohe Temperaturen eignen sich vorteilhaft das Thermokompressionsbonden mit AgPd auf Pt oder Spaltschweißen mit Pt- bzw. Ni-Drähten auf Pt bzw. Ni.For temperatures up to 5000C, platinum is alone, even at atmospheric Environment, in a vacuum, Ni is advantageous up to over 6000C. For contacting high Temperatures are advantageous thermocompression bonding with AgPd on Pt or gap welding with Pt or Ni wires on Pt or Ni.
Je nach TCR und K-Faktor eignen sich solche Schichten vorteilhaft für Dehnungsmeßstreifen (TCRfO) oder Widerstände mit positivem oder negativem Temperaturkoeffizienten zur Temperaturmessung. Außerdem eignen sie sich vorteilhaft für die Herstellung von Leiterbahnen hoher mecbachnischer Stabilität sowie als Material für Heizwendel, wie sie beispielsweise vorteilhaft für Halbleitergassensoren benötigt werden.Such layers are advantageous depending on the TCR and K factor for strain gauges (TCRfO) or resistors with positive or negative temperature coefficients for temperature measurement. In addition, they are advantageously suitable for manufacture of conductor tracks with high mechanical stability and as a material for heating coils, as they are advantageously required for semiconductor gas sensors, for example.
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Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
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EP0241874A2 (en) * | 1986-04-11 | 1987-10-21 | AT&T Corp. | Device including a temperature sensor |
DE3817905A1 (en) * | 1987-05-27 | 1988-12-08 | Ngk Insulators Ltd | MOLD CHANGE PROBE |
WO1995017533A1 (en) * | 1993-12-23 | 1995-06-29 | Mayer, Isabella, Veronika | Material of chemical compounds with a metal in group iv a of the periodic system, nitrogen and oxygen and process for producing it |
US5670248A (en) * | 1994-07-15 | 1997-09-23 | Lazarov; Miladin P. | Material consisting of chemical compounds, comprising a metal from group IV A of the periodic system, nitrogen and oxygen, and process for its preparation |
EP1029943A1 (en) * | 1999-02-17 | 2000-08-23 | Nihon Shinku Gijutsu Kabushiki Kaisha | Process for producing barrier film |
DE10153424A1 (en) * | 2001-11-03 | 2003-05-15 | Kmw Duennschichttechnik Und Mi | Pressure transducers, in particular for measuring cylinder pressure in engines and methods for producing the same |
WO2007048613A1 (en) * | 2005-10-28 | 2007-05-03 | Kmw Kaufbeurer Mikrosysteme Wiedemann Gmbh | Sensor with resistance layer |
WO2009129930A1 (en) * | 2008-04-24 | 2009-10-29 | Hochschule Für Technik Und Wirtschaft Des Saarlandes | Film resistor with a constant temperature coefficient and production of a film resistor of this type |
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DE102016108985A1 (en) | 2016-05-13 | 2017-11-16 | Trafag Ag | Method for producing a sensor element by means of laser structuring |
DE102017108582A1 (en) | 2017-04-21 | 2018-10-25 | Epcos Ag | Sheet resistance and thin film sensor |
DE102017114228B4 (en) * | 2017-06-27 | 2021-05-20 | Tdk Electronics Ag | Sheet resistor and thin film sensor |
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Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
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EP0241874A3 (en) * | 1986-04-11 | 1989-05-24 | AT&T Corp. | Device including a temperature sensor |
EP0241874A2 (en) * | 1986-04-11 | 1987-10-21 | AT&T Corp. | Device including a temperature sensor |
DE3817905A1 (en) * | 1987-05-27 | 1988-12-08 | Ngk Insulators Ltd | MOLD CHANGE PROBE |
CN1070933C (en) * | 1993-12-23 | 2001-09-12 | 米莱丁·P·拉扎洛夫 | Compound material containing metal in IVB group of periodic table, nitrogen and oxygen and preparation method thereof |
WO1995017533A1 (en) * | 1993-12-23 | 1995-06-29 | Mayer, Isabella, Veronika | Material of chemical compounds with a metal in group iv a of the periodic system, nitrogen and oxygen and process for producing it |
DE4344258C1 (en) * | 1993-12-23 | 1995-08-31 | Miladin P Lazarov | Material from chemical compounds with a metal of group IV A of the periodic table, nitrogen and oxygen, its use and production method |
US5670248A (en) * | 1994-07-15 | 1997-09-23 | Lazarov; Miladin P. | Material consisting of chemical compounds, comprising a metal from group IV A of the periodic system, nitrogen and oxygen, and process for its preparation |
EP1029943A1 (en) * | 1999-02-17 | 2000-08-23 | Nihon Shinku Gijutsu Kabushiki Kaisha | Process for producing barrier film |
KR100773280B1 (en) * | 1999-02-17 | 2007-11-05 | 가부시키가이샤 알박 | Barrier film and method of manufacturing the same |
DE10153424A1 (en) * | 2001-11-03 | 2003-05-15 | Kmw Duennschichttechnik Und Mi | Pressure transducers, in particular for measuring cylinder pressure in engines and methods for producing the same |
WO2007048613A1 (en) * | 2005-10-28 | 2007-05-03 | Kmw Kaufbeurer Mikrosysteme Wiedemann Gmbh | Sensor with resistance layer |
WO2009129930A1 (en) * | 2008-04-24 | 2009-10-29 | Hochschule Für Technik Und Wirtschaft Des Saarlandes | Film resistor with a constant temperature coefficient and production of a film resistor of this type |
US8198978B2 (en) | 2008-04-24 | 2012-06-12 | Hochschule fur Technik und Wirtschaft des Sarlandes | Film resistor with a constant temperature coefficient and production of a film resistor of this type |
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