CN102117670B - Resistor material, resistance film form by sputtering target, resistance film, thin film resistor and their manufacture method - Google Patents
Resistor material, resistance film form by sputtering target, resistance film, thin film resistor and their manufacture method Download PDFInfo
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Abstract
Even if the object of this invention is to provide also all good thin film resistor and resistor material and manufacture methods for the manufacture of described thin film resistor of resistivity, resistance-temperature characteristic, high-temperature stability, resistance to salt water of a kind of heat treatment through relative low temperature. The invention provides a kind of resistor material, this resistor material is the silicate Glass that is added with 3～20 quality % in Ni alloy, wherein, the a kind of above interpolation element in Cr, Al and Y that is selected from that this Ni alloy contains 10～60 quality %, and surplus is Ni and unescapable impurity, and this silicate Glass is with SiO2For main component, and contain 0～90 quality % be selected from B, Mg, Ca, Ba, Al, Zr and their oxide more than a kind.
Description
Technical field
The present invention relates to as the thin film resistor of electronic unit and for obtaining this thin film resistorResistance film, the sputtering target that this resistance film forms use, the resistor material that forms this sputtering target,Further, also relate to their manufacture method.
Background technology
The thin film resistor that uses resistance film, has been applied to chip resister, precision resistor, netNetwork resistor, high-voltage resistor constant resistance device; Temperature detecting resistance body, temperature-sensitive resistor equitemperature sensor;And in the electronic unit of hydrid integrated circuit and composite module goods thereof etc.
For thin film resistor, require to have 4 characteristics: (1) temperature-coefficient of electrical resistance (TCR)Absolute value approach 0 resistance-temperature characteristic; (2) high temperature keep time through time resistance change rate littleHigh-temperature stability; (3) corrosion resistance of sweat or the seawater etc. to people (resistance to salt water); (4)Resistivity is high.
Be accompanied by the propelling of the miniaturization of electric and electronic goods, expecting thin film resistor to carry out littleType, but for the miniaturization of this thin film resistor, need to keep above-mentioned characteristic and further improveForm the resistivity of the resistor material of resistance film.
In thin film resistor, in most cases, as the resistor material that is used to form resistance film,Mainly adopt Ta alloy, TaN compound, Ni-Cr to be associated gold etc.
Wherein, use Ni-Cr to be associated golden resistance film, possessed and have as metallic characterOhm property (ohmiccharacteristics), resistance value occur with respect to variation of ambient temperatureChange feature little and that heat endurance is high, therefore, be conventionally applied to thin film resistor. But,Ni-Cr is associated gold as resistor material, has the problem that resistivity is low.
Therefore, someone has proposed a kind of resistance film, and it is that Ta, Al, Mo are made an addition to Ni-Cr is associated in gold, to improve resistivity (with reference to patent documentation 1). By this be added with Ta, Al,The Ni-Cr of Mo is associated the resistance film that gold obtains, and is associated golden electricity with use Ni-Cr in the pastResistance film is compared, and excellent corrosion resistance still, is adopting acid synthetic perspiration (JISL0848)Electrolytic corrosion test in dissolving starting voltage for being less than 6V, therefore, expect to have corrosion resistance moreGood resistance film.
In addition, this Ni-Cr is associated gold, imposes heat treatment in order to obtain the characteristic of regulation, by instituteNeed characteristic requirements to heat-treat with the high temperature that is greater than 500 DEG C. Therefore, described in needing further to reduceHeat treatment temperature.
Background technology document
Patent documentation 1: TOHKEMY 2008-10604 communique
Summary of the invention
The object of the present invention is to provide a kind of thin film resistor, even if it carries out resistance with lower temperatureIn the heat treated situation of film, also can keep and the above-mentioned Ni-Cr that is added with Ta, Al, MoBe associated the same high resistivity of metallographic, good resistance-temperature characteristic, high-temperature stability, and there is heightCorrosion resistance.
Resistor material of the present invention, is characterized in that, in Ni alloy, is added with 3～20 matterAmount % silicate Glass, wherein, this Ni alloy contain 10～60 quality % be selected from Cr,In Al and Y a kind above interpolation element, and surplus is Ni and unescapable impurity, shouldSilicate Glass is with SiO2(silica) is main component, and contains 0～90 quality %Be selected from B, Mg, Ca, Ba, Al, Zr and their oxide more than a kind.
Resistance film of the present invention forms the sputtering target of use, is to obtain by following manner: so that silicic acidSalt glass frit end is that the mode of 3～20 quality % is by silicate Glass powder and Ni alloy powderMix, make obtained mixed-powder be shaped to required shape, and make obtained formed body veryIn sky or non-active gas environment, with 50kg/cm2Above adding depressed, and enters with 500～1400 DEG CRow sintering, wherein, this silicate Glass powder is with SiO2For main component, and be added with 0～90 quality % be selected from B, Mg, Ca, Ba, Al, Zr and their oxide more than a kind,1 kind of above the adding in Cr, Al and Y that is selected from that this Ni alloy powder contains 10～60 quality %Added elements, and surplus is Ni and unescapable impurity.
The composition of this kind of sputtering target is in fact identical with above-mentioned resistor material.
Resistance film of the present invention, adopts above-mentioned sputtering target, by sputtering method on insulating materials substrateForm film, by obtained film in atmosphere or in non-active gas environment, with 200～500DEG C heat-treat and to obtain for 1～10 hour.
The composition of this kind of resistance film, also with the resistor material phase in fact that forms above-mentioned sputtering targetWith.
Resistance film of the present invention has following characteristic: resistivity is 300～1500 μ Ω Gm, electricityResistance temperature coefficient, in the scope of-25～+ 25ppm/ DEG C, keeps 1000 hours 155 DEG C of high temperatureIn through time resistance change rate be below 0.1%, and, adopt acid synthetic perspiration (JISL0848)Electrolytic corrosion test in dissolving starting voltage be more than 9V.
Thin film resistor of the present invention, is characterized in that, is by insulating materials substrate, at this insulation materialThe both sides of the resistance film forming on material substrate, this resistance film on this insulating materials substrate formElectrode form, described resistance film has above-mentioned resistance film characteristic.
Resistance film material of the present invention is used as sputtering target, give film forming by sputtering method andObtain resistance film, use the thin film resistor of this resistance film, can realize 300 simultaneously～The high resistivity of 1500 μ Ω cm, the absolute value of temperature-coefficient of electrical resistance are in ± 25ppm/ DEG C scopeGood resistance-temperature characteristic, 155 DEG C of high temperature keep in 1000 hours through time resistance change rateBe the higher high-temperature stability below 0.1% and adopt acid synthetic perspiration (JISL0848)Electrolytic corrosion test in dissolving starting voltage be highly corrosion resistant (resistance to salt water) more than 9V.
Also, according to the present invention, can be by high resistance, electronic unit that high-temperature stability is good, shouldFor to excellent corrosion resistance than more having under the harsh and unforgiving environments of requirement in the past, and above-mentioned characteristic can be withHeat treatment lower than the past temperature obtains, and therefore, the present invention also helps the system that makes thin film resistorMake cost degradation.
Brief description of the drawings
Fig. 1 is the synoptic diagram of the applicable thin film resistor of the present invention.
Fig. 2 is the synoptic diagram that represents electrolytic corrosion test.
The explanation of Reference numeral
1 insulating properties substrate (aluminum oxide substrate)
2 resistance films
3 electrodes (Au electrode)
4 drops
Detailed description of the invention
Thin film resistor requires there is so-called high resistance, stable resistance-temperature characteristic, good high temperature are steadyQualitative and 4 characteristics of highly corrosion resistant (resistance to salt water), in order to improve described characteristic with Ni-Cr has carried out various trials centered by being associated gold.
Be associated at Ni-Cr the Ni-Cr that is added with Ta, Al and Mo in gold and be associated gold, withPast alloy phase ratio, is still keeping original resistance-temperature characteristic and high-temperature stability, and is trying to achieveTo the improvement of resistance and corrosion resistance. But, say as above-mentioned, obtain this specific character (specialTo make the scope of temperature-coefficient of electrical resistance in regulation), need to will adopt above-mentioned resistor material to formThe film of film is heat-treated 1～10 hour with the temperature of 200～600 DEG C, according to desirable characteristics,Need to heat-treat with higher temperature (high temperature temperature on one side), in the hope of maintenance or furtherImproving above-mentioned characteristic, is can be with lower temperature (low temperature on one side temperature) but more people expectThe resistor material of heat-treating.
The inventor etc. by the result repeatedly studying intensively are: do not adopt and be applied to electronic unit in the pastWith the resistor material of thin film resistor, and just measure in accordance with regulations in Ni alloy and add silicateGlass, thus, can relatively reduce the heat treatment temperature for obtaining desirable characteristics, and, energyEnough above-mentioned characteristics (particularly corrosion resistance) of further improving. According to above-mentioned result of study, the present inventionPeople etc. the present invention.
Resistor material of the present invention, is characterized in that: in Ni alloy, be added with 3～20 matterAmount % silicate Glass, wherein, this Ni alloy contain 10～60 quality % be selected from Cr,In Al and Y a kind above interpolation element, and surplus is Ni and unescapable impurity, shouldSilicate Glass is with SiO2(silica) is main component, and contains 0～90 quality %Be selected from B, Mg, Ca, Ba, Al, Zr and their oxide more than a kind.
This resistor material is to have the resistive element material that is characterized as feature being had with above-mentioned compositionMaterial, it is as long as having identical in fact composition, to not restriction of mode. Therefore, originallyThe term of the resistor material in invention, be to resistance film form process in from raw material toThe general designation that all modes till resistance film are done.
Ni alloy is from substantially having formed resistor material of the present invention. This Ni alloy contains 10～60 quality % are selected from Cr, Al and Y a kind above interpolation element, and surplus is NiWith unescapable impurity.
Add element and there is the reduction that various effects: Cr is conducive to the absolute value of temperature-coefficient of electrical resistance,Al is conducive to the raising of corrosion resistance, and Y is conducive to the adhering raising of Ni alloy and glass powder.These add element, only add requirement according to desired characteristic, but in order to possess the present applicationThin film resistor in characteristic, be preferably and contain all interpolation elements. In order to bring into play various characteristics,Need to contain respectively Cr is that 10 quality % are above, Al is that 10 quality % are above, Y is 0.3 quality %Above, and, need to make more than it counts 10 quality % by total amount. When adding the addition of elementCount in the situation that is less than 10 quality % by total amount, the resistivity of the resistance film obtaining can not becomeFor enough large. On the other hand, when these add elements when too much, can cause steady after film forming, heatingQualitative variation, reproducibility variation, therefore, need to be set as by below total amount 60 quality %.From reducing the viewpoint of absolute value of temperature-coefficient of electrical resistance, be preferably set to the total amount place that adds elementIn the scope of 40～50 quality %. Temperature-coefficient of electrical resistance, both the composition based on glass described later occurredChange, also the composition based on Ni alloy changes. Consider from this point, preferably to Ni alloyAdding element total amount is 40～50 quality %.
Resistor material of the present invention, is characterized in that, in this Ni alloy, be added with 3～The silicate Glass of 20 quality %, this silicate Glass is with SiO2(silica) is mainComposition, what contain 0～90 quality % is selected from B, Mg, Ca, Ba, Al, Zr and their oxygenIn compound more than a kind.
Silicate Glass is mainly the effect with the resistance value that improves resistance film. In addition, alsoBe improved the effect of the corrosion resistance of resistance film. Further, by containing silicate Glass,Can relatively reduce the heat treatment temperature that the film after film forming is carried out in order to obtain required characteristic.
Silicate Glass is insulator, therefore, even if there is a small amount of interpolations more than 3 quality % also canObtain its effect. On the contrary, in the time that being greater than 20 quality %, addition can become insulator, and can not be byCarry out film forming in DC sputter, therefore have the problem of cost aspect. In addition adding of silicate Glass,Dosage, is preferably the scope of 5～10 quality %.
In silicate Glass, as additive, contain be selected from B, Mg, Ca, Ba, Al,In Zr and their oxide more than a kind. Wherein, the content of these additives, is set asBelow 90 quality %. In the time that the content of this additive is greater than 90 quality %, can cause resistance temperatureThe absolute value of coefficient can not be within the scope of ± 25ppm/ DEG C.
By adding these B, Mg, Ca, Ba, Al, Zr or their oxide, can carry outThe fusion temperature of resistance film, the fine setting of resistance to water. In addition, by Al or aluminium oxide (Al2O3)Interpolation, can suppress resistance film phase-splitting occur. But the present invention is not subject to these additivesImpact, above-mentioned is only that additive to containing in silicate Glass gives example, completelyThe silicate Glass that does not contain these additives also can be applicable to the present invention. In addition, from silicateThe crystalline viewpoint of glass is set out, when add in the situation of this additive, be preferably comprise wholeB, Mg, Ca, Ba, Al, Zr. In addition, from the same reason, also comprise that they are oxygenThe situation of compound, and wish that its total amount is set as the scope of 30～70 quality %.
Sometimes expect as required, after sintering is carried out in hot pressing described later, adjust these additivesAnd addition, so that non-crystallizableization of silicate Glass. Its reason is, when silicate Glass is sent outWhen raw crystallization, can cause that the density of resistor material does not rise and strength decreased, be undertaken by sputterWhen film forming, there will be problem.
Next, resistance film formation of the present invention is described with the making of sputtering target. This spatteringIn the raw material of shooting at the target, use silicate Glass powder and Ni alloy powder, wherein, described siliconPhosphate-gallate series glass powder is with SiO2For main component, and be added with 0～90 quality % be selected from B,In Mg, Ca, Ba, Al, Zr and their oxide more than a kind, described Ni alloyed powderBeing selected from Cr, Al and Y of 30～60 quality % (being preferably 40～50 quality %) contained at end1 kind of above interpolation element, and surplus is Ni and unescapable impurity.
As the Ni alloy powder that is material powder, preferably using average grain diameter is 10～200 μ m,Within being preferably the scope in 30～150 μ m, be more preferably the spherical mist of 100 μ m left and rightChange powder. In addition, as silicate Glass powder, preferably using average grain diameter is 0.5～50 μ m,Within being preferably the scope in 1～30 μ m, be more preferably the powder of 10 μ m left and right.
From making the angle of material powder sintering, conventionally wish for the thin material powder of particle diameter. But,In the time carrying out sintering by hot pressing, be not limited to this. Its reason is, in the time of hot pressing, in carbonaceous mouldBe filled with material powder, but there is gap in joint in carbonaceous mould, therefore, when material powder mistakeWhen thin, material powder can spill from gap, has reduced machinability.
On the other hand, when the average grain diameter of Ni alloy powder is for being greater than 200 μ m, or silicateThe average grain diameter of glass powder is to be greater than in the situation of 50 μ m, and the problem that target density reduces can occur.
These raw material are carried out to dry type mixing, so that above-mentioned silicate Glass powder is 3～20Quality % (being preferably 5～10 quality %), obtains as the mixed-powder of material powder, by obtainThe mixed-powder obtaining is shaped to required shape, and obtained formed body is preferably made to its burning with pressure sinteringKnot, thus, can obtain above-mentioned sputtering target. As concrete sintering condition, preferably in vacuum or non-In active gas environment, at 50kg/cm2Above adding depressed, 500～1400 DEG C of roastings 1～5Hour, make it thus sintering. In pressure sintering in this description, also comprise HIP (waiting quiet hot pressing)Method. When pressurization is less than 50kg/cm2, roasting time is less than in the situation of 1 hour, can not obtain highThe target of density. On the other hand, even if exceed the hot pressing of 5 hours, can not obtain further and carryHighdensity effect.
For sintering temperature, wish higher than the softening point of glass powder, and lower than the fusing point of Ni alloy.The sintered body so obtaining, prepares size dimension as required, comes by joint (bonding) etc.Obtain sputtering target.
Then, the making of resistance film of the present invention is described. Acquisition is as mentioned above pressed in useSputtering target, while carrying out film forming, obtains and resistor material same composition thin in fact by sputtering methodFilm. As substrate now, hope is Al2O3、SiO2Deng insulator substrate. In addition, exceptOutside sputtering method, also resistor material of the present invention can be processed as to sheet for evaporation (タ Block レ Star ト),Make resistance film film forming by vapour deposition methods such as vacuum evaporations.
For sputtering method, be not subject to the restriction of its kind, but from the sight of cost aspect and productionPoint sets out, and preferably adopts DC sputter. Although sputtering condition also arranges according to sputter equipment,That for example, the size that adopts target is that sputtering target, the power output of φ 75mm × 3mm is 200WIn the situation of the sputter equipment of (fixing), voltage be 400～600V, electric current be 0.3～0.5A,Ar flow is that 15～25SCCM, gross pressure are that 0.4～0.6Pa, TS distance is (from target to substrateDistance) be under the condition of 85mm, carry out film forming.
For the film that only carries out spatter film forming, temperature-coefficient of electrical resistance becomes large negative value, and then at high temperatureIn resistance stability insufficient. Therefore, according to the film composition after film forming, need to be in atmosphere or non-In active gases, heat-treat 1～10 hour at 200～500 DEG C. By this heat treatment, canObtain the absolute value of temperature-coefficient of electrical resistance for to be less than ± resistance film of 25ppm/ DEG C.
In the time that heat treatment temperature is less than 200 DEG C, the temperature-coefficient of electrical resistance shakiness of the resistance film obtainingFixed, on the other hand, in the time that heat treated temperature is greater than 500 DEG C, the temperature-coefficient of electrical resistance of resistance filmBecome large on the occasion of. In addition, under heat treatment time is less than the situation of 1 hour, the resistance obtainingThe temperature-coefficient of electrical resistance of film is unstable, on the other hand, and the feelings that are greater than 10 hours when heat treatment timeUnder condition, also, there are no the effect of improving that further increases temperature-coefficient of electrical resistance stability, but strengthen for this reasonCost.
In addition,, in the composition of resistor material of the present invention, this heat treatment temperature is added with having usedThe Ni-Cr that is added with Ta, Al and Mo is associated the situation of golden resistance film and compares, and relatively reduces.Particularly, be associated golden in the situation that at this Ni-Cr, according to composition, sometimes for obtaining required spySexual needs are heat-treated under the high temperature that is greater than 500 DEG C, but in the group of resistor material of the present inventionOne-tenth aspect, can become 500 DEG C below and can make the heat treatment temperature in whole compositing range move toLow temperature (low temperature temperature on one side).
In addition, aspect characteristic, resistance film of the present invention, maintains characteristic same,Particularly, aspect corrosion resistance (resistance to salt water), can obtain and adopt acid synthetic perspiration (JISL0848) the dissolving starting voltage in electrolytic corrosion test is better effect more than 9V.
Thin film resistor of the present invention, as shown in Figure 1, is by insulating materials substrate (1), formsResistance film (2) thereon and be formed at the resistance film (2) on insulating materials substrate (1)The electrode (3) of both sides forms. As electrode (3), except Au electrode, also can use Al,The electrodes such as Ag, Cu, Ni, Cr. This thin film resistor, has according to resistance film of the present inventionAnd the characteristic having.
Embodiment
Embodiment 1
As Ni alloy powder, prepare by total amount 40 quality % and added Cr, Al and Y (Cr: Al: Y=29.5: 10.0: 0.5 (mass ratio)) average grain diameter is the Ni alloy powder of 100 μ m. AnotherAspect, as silicate Glass powder, prepared by total amount 50 quality % add B, Mg, Ca,The average grain diameter of Ba, Al and Zr (B: Mg: Ca: Ba: Zr: Al=2: 5: 18: 18: 5: 2 (mass ratio))Be the SiO of 10 μ m2Powder.
These 2 kinds of powder are mixed and make the addition of silicate Glass powder is 5 quality %, formsMaterial powder.
This material powder is packed in the carbonaceous mould of required form, adopt Guang Zhu Co., Ltd. (strain formulaThe Wide Building of commercial firm) manufacture atmosphere hot pressing furnace (AHP) carry out hot pressing. Flow with 2L/min at ArIn non-active gas environment, at so-called 200kg/cm2Pressure, the sintering temperature, 3 little of 1100 DEG CTime the condition of roasting time under, make this formed body sintering and obtain sintered body.
Adopt surface grinding machine (PSG-105DX, Co., Ltd.'s this work mechanism of ridge is made manufacturing)The sintered body that machining obtains and make thickness be 3.0mm after, adopt wire cutting machine tool (ワ イ ヤ mono-カStar ト, AQ750L, the ソ デ イ of Co., Ltd. Star Network is manufactured) to process and make diameter be 75.0mm, then,Use containing indium scolder buck plate (BuckingPlate) and sintered body are bonded together and form sputterTarget.
DC sputter equipment (CFS-4ES, sesame Pu メ カ ト will be installed on as the above-mentioned sputtering target obtainingロ ニ Network ス Co., Ltd. manufactures) upper, and make TS distance (distance from target to substrate) for 85mm,Be vented to 5 × 10-4After pa, importing purity is more than 99.999% Ar gas, is held in 0.5PaPressure, taking sputtering power as 200W, voltage carry out sputter as 500V, electric current as 0.4A so thatThickness is 100nm, and on substrate, film forming is the film of 20mm × 25mm size. Substrate nowUse Al2O3。
At the two ends of obtained film, adopting same DC sputtering method to carry out film forming is thickness 500nmAu electrode. Then, in atmospheric environment, heat-treat 3 hours with the temperature of 300 DEG C, obtainMust use the thin film resistor of resistance film of the present invention.
About obtained thin film resistor, carried out resistivity described as follows, resistance-temperature characteristic,The evaluation of high-temperature stability and corrosion resistance (resistance to salt water).
About resistivity, be by adopting resistrivity meter (ロ レ ス タ GPMCP-T610 type, strain formulaThe ア of Mitsubishi Chemical of commercial firm Na リ Star Network is manufactured), detect and obtain by four-point probe method at room temperature.In the present invention, be that more than 300 μ Ω cm thin film resistor is judged as good merchantable brand by thering is resistivity.
About resistance-temperature characteristic, be that obtained thin film resistor is inserted in constant temperature mortise, to 25 DEG CAdopt above-mentioned resistrivity meter to detect with the resistance value (unit: Ω) in 125 DEG C, by obtainResistance value calculate temperature-coefficient of electrical resistance, evaluate thus. In the present invention, by resistance temperature beThe thin film resistor of number within the scope of ± 25ppm/ DEG C is judged as good merchantable brand.
About high-temperature stability, be that obtained thin film resistor is kept in the thermostat of 155 DEG C1000 hours, adopt above-mentioned resistrivity meter to detect the resistance value (unit: Ω) before and after it, by obtainThe resistance value obtaining calculates resistance change rate (155 DEG C, 1000 hours), evaluates thus. ThisIn invention, to be placed in thermostat resistance value before as benchmark, by the resistance value ratio after inserting beThin film resistor below 0.1% is judged as good merchantable brand.
About resistance to salt water, be that obtained thin film resistor is carried out to following electrolytic corrosion test, detectDissolve starting voltage, evaluate thus.
First, adopt digital multimeter (デ ジ タ Le マ Le チ メ mono-タ) (VOAC7521A, rockTong Meter Measuring Co., Ltd. (rock logical measure Co., Ltd.) manufactures), according to four-end method to resistance film (2)Initial stage resistance value detect. Then, as shown in Figure 2, use micro syringe in resistance film (2)Central authorities drip the 30 acid synthetic perspirations of μ L (JISL0848), from the diameter of drop (4) andLength between Au electrode (3) is set out, and adjusts the voltage (Vp) between Au electrode (3),Be 1V so that be carried on the voltage (Vd) at drop (4) two ends. By between Au electrode (3)Voltage (Vp) is made as necessarily,, after 3 minutes, washes and is dried, according to four at load voltageHold-carrying detection resistance value, the resistance change rate before and after detection voltage loads.
Voltage (Vp) between adjustment Au electrode (3) is so that be carried on the electricity at drop (4) two endsPress (Vd) to rise and repeatedly carry out above-mentioned detection with the amplitude of 0.2V from 1V, thus, obtain electricityThe voltage (Vd) of drop (4) the two ends institute load of resistive rate when being greater than 0.2% is as resistanceThe dissolving starting voltage of film (2).
Therefore the dissolving starting voltage, obtaining is the drop two ends detected while meeting following conditionMinimum of a value in voltage: with certain voltage, to dripping after acid synthetic perspiration (JISL0848)Load voltage 3 minutes between the Au electrode at two ends, after washing and being dried, the resistance variations of detectionRate is for being greater than 0.2%. In the present invention, be thin film resistor more than 9.0V by dissolving starting voltageBe judged as good merchantable brand.
Embodiment 2
Be 3 quality % except making the addition of silicate Glass powder, similarly to Example 1Ground carries out and obtains thin film resistor, and its characteristic is detected.
Embodiment 3
Be 10 quality % except making the addition of silicate Glass powder, with embodiment 1 withCarry out sample and obtain thin film resistor, its characteristic is detected.
Embodiment 4
Be 20 quality % except making the addition of silicate Glass powder, with embodiment 1 withCarry out sample and obtain thin film resistor, its characteristic is detected.
Embodiment 5
Except not to adding additive in silicate Glass powder (in silicate Glass powderThe content of additive is 0 quality %) in addition, carry out similarly to Example 1 and obtain film resistorDevice, detects its characteristic.
Embodiment 6
Be 30 quality % except making the content of the additive in silicate Glass powder, with realityExecute example 1 similarly to carry out and obtain thin film resistor, its characteristic is detected.
Embodiment 7
Be 70 quality % except making the content of the additive in silicate Glass powder, with realityExecute example 1 similarly to carry out and obtain thin film resistor, its characteristic is detected.
Embodiment 8
Be 90 quality % except making the content of the additive in silicate Glass powder, with realityExecute example 1 similarly to carry out and obtain thin film resistor, its characteristic is detected.
Embodiment 9
Be 10 quality % except making the content of the interpolation element in Ni alloy, with embodiment 1 withCarry out sample and obtain thin film resistor, its characteristic is detected.
Embodiment 10
Be 30 quality % except making the content of the interpolation element in Ni alloy, with embodiment 1 withCarry out sample and obtain thin film resistor, its characteristic is detected.
Embodiment 11
Be 50 quality % except making the content of the interpolation element in Ni alloy, with embodiment 1 withCarry out sample and obtain thin film resistor, its characteristic is detected.
Embodiment 12
Be 60 quality % except making the content of the interpolation element in Ni alloy, with embodiment 1 withCarry out sample and obtain thin film resistor, its characteristic is detected.
Comparative example 1
Except not adding silicate Glass powder, carry out similarly to Example 1 and obtainThin film resistor, detects its characteristic. The resistivity of the thin film resistor of comparative example 1 is littleIn 300 μ Ω cm, resistance change rate for being greater than 0.1%, and dissolve starting voltage very low. ByThis understands, and when obtaining in the situation that heat treatment temperature when resistance film is relatively low, can not obtain and possessThe thin film resistor of characteristic fully.
Comparative example 2
Be 30 quality % except making the addition of silicate Glass powder, with embodiment 1 withCarry out sample, obtain sputtering target. But, when intending to adopt this sputtering target to enter similarly to Example 1When the film forming of row resistance film, because the electric conductivity of target is insufficient, so do not have can film forming.
Comparative example 3
Be 95 quality % and setting silicon except making the content of the additive in silicate Glass powderThe addition of phosphate-gallate series glass powder is beyond 10 quality %, carries out similarly to Example 1 and obtainsObtain thin film resistor, its characteristic is detected. For the thin film resistor of comparative example 3,The scope of exceed ± 25ppm/ of temperature-coefficient of electrical resistance DEG C, dissolves starting voltage in addition for being less than 9V, byThis understands, and it can not reach resistance-temperature characteristic of the presently claimed invention and corrosion resistance.
Comparative example 4
Be 0 quality % except making the content of the interpolation element in Ni alloy, with embodiment 1 withCarry out sample and obtain thin film resistor, its characteristic is detected. For the film of comparative example 4Resistor, resistivity is for being less than 300 μ Ω cm, and temperature-coefficient of electrical resistance is exceed ± 25ppm/ DEG CScope, and dissolve starting voltage for being less than 9V, thus understanding, it can not reach institute of the present inventionThe resistance, resistance-temperature characteristic, the corrosion resistance that require.
Comparative example 5
Be 70 quality % except making the content of the interpolation element in Ni alloy, with embodiment 1 withCarry out sample and obtain thin film resistor, its characteristic is detected. For the film of comparative example 5Resistor, temperature-coefficient of electrical resistance for to exceed ± scope of 25ppm/ DEG C, and dissolve starting voltageFor being less than 9v, to understand thus, it can not reach resistance-temperature characteristic of the presently claimed invention and resistance toCorrosivity.
Various compositions in each embodiment, DC sputter could, film thermal treatment temperature after film formingAnd the testing result of the thin film resistor characteristic obtaining, be shown in table 1.
Table 1
Embodiment 13
Except adopting by total amount 50 quality %, adds in the silicate Glass powder as in material powderThere are Mg, Ca, Ba, Al and Zr (Mg: Ca: Ba: Zr: Al=5: 20: 18: 5: 2 (mass ratioes))Average grain diameter is the SiO of 10 μ m2Beyond powder, carry out similarly to Example 1 and obtain filmResistor, detects its characteristic.
Embodiment 14
Be 7 quality % except making the addition of silicate Glass powder, with embodiment 13 withCarry out sample and obtain thin film resistor, its characteristic is detected.
Embodiment 15
Be 10 quality % except making the addition of silicate Glass powder, with embodiment 13 withCarry out sample and obtain thin film resistor, its characteristic is detected.
Embodiment 16
Except not to adding additive in silicate Glass powder (in silicate Glass powderThe content of additive is 0 quality %) in addition, carry out similarly to Example 13 and obtain thin-film electroResistance device, detects its characteristic.
Embodiment 17
Be 90 quality % except making the content of the additive in silicate Glass powder, with realityExecute example 13 similarly to carry out and obtain thin film resistor, its characteristic is detected.
Embodiment 18
Be 50 quality % except making the content of the interpolation element in Ni alloy, with embodiment 13Similarly carry out and obtain thin film resistor, its characteristic is detected.
Comparative example 6
Except not adding silicate Glass powder, carry out similarly to Example 13 and obtainObtain thin film resistor, its characteristic is detected.
Comparative example 7
Be 30 quality % except making the addition of silicate Glass powder, with embodiment 13 withCarry out sample and obtain thin film resistor, its characteristic is detected.
Comparative example 8
Be 95 quality % and setting silicon except making the content of the additive in silicate Glass powderThe addition of phosphate-gallate series glass powder is beyond 10 quality %, carries out similarly to Example 13 and obtainsObtain thin film resistor, its characteristic is detected.
Comparative example 9
Be 0 quality % except making the content of the interpolation element in Ni alloy, with embodiment 13 withCarry out sample and obtain thin film resistor, its characteristic is detected.
Comparative example 10
Be 70 quality % except making the content of the interpolation element in Ni alloy, with embodiment 13Similarly carry out and obtain thin film resistor, its characteristic is detected.
In comparative example 6～10, also can see the trend same with comparative example 1～5.
Various compositions in each embodiment, DC sputter could, film thermal treatment temperature after film formingAnd the testing result of the thin film resistor characteristic obtaining, be shown in table 2.
Table 2
Claims (7)
1. a resistor material, it is that to be formed for obtaining the resistance film of thin film resistor usedResistor material; It is characterized in that, in Ni alloy, be added with the silicate of 3～20 quality %Be glass,
The interpolation element that is selected from Cr, Al and Y that this Ni alloy contains 10～60 quality %, andCr is that 10 quality % are above, Al is that 10 quality % are above, Y is more than 0.3 quality %, and more thanAmount is Ni and unescapable impurity,
This silicate Glass is with SiO2For main component and contain 0～90 quality % be selected from B,In Mg, Ca, Ba, Al, Zr and their oxide more than a kind.
2. a resistance, diaphragm formation sputtering target, it is formed for obtaining thin film resistorThe resistance, diaphragm formation sputtering target that resistance film is used; It is characterized in that, in Ni alloy,Be added with the silicate Glass of 3～20 quality %,
The interpolation element that is selected from Cr, Al and Y that this Ni alloy contains 10～60 quality %, andCr is that 10 quality % are above, Al is that 10 quality % are above, Y is more than 0.3 quality %, and more thanAmount is Ni and unescapable impurity,
This silicate Glass is with SiO2For main component and contain 0～90 quality % be selected from B,In Mg, Ca, Ba, Al, Zr and their oxide more than a kind.
3. a resistance film, it is the resistance film for obtaining thin film resistor; Its feature existsIn, in Ni alloy, be added with the silicate Glass of 3～20 quality %,
The interpolation element that is selected from Cr, Al and Y that this Ni alloy contains 10～60 quality %, andCr is that 10 quality % are above, Al is that 10 quality % are above, Y is more than 0.3 quality %, and more thanAmount is Ni and unescapable impurity,
This silicate Glass is with SiO2For main component and contain 0～90 quality % be selected from B,In Mg, Ca, Ba, Al, Zr and their oxide more than a kind; And,
The resistivity of this resistance film is 300～1500 μ Ω cm, temperature-coefficient of electrical resistance in-25～The scope of+25ppm/ DEG C, 155 DEG C of high temperature keep in 1000 hours through time resistance change rate beBelow 0.1%, and, adopt according to the acid synthetic perspiration's of JISL0848 standard electrolytic corrosion testIn dissolving starting voltage be more than 9V.
4. a thin film resistor, is characterized in that, it is by insulating materials substrate, at this insulation materialThe resistance film claimed in claim 3 forming on material substrate and being somebody's turn to do on this insulating materials substrateThe electrode that the both sides of resistance film form forms.
5. resistance film forms the manufacture method with sputtering target, it is characterized in that, so that silicic acidSalt glass frit end is that the mode of 3～20 quality % is mixed silicate Glass powder and Ni alloy powderClose, make obtained mixed-powder be shaped to required form, and make obtained formed body in vacuum orIn non-active gas environment, at 50kg/cm2Above adding depressed, and carries out sintering at 500～1400 DEG C,
Wherein, this silicate Glass powder is with SiO2For main component and be added with 0～90 quality% be selected from B, Mg, Ca, Ba, Al, Zr and their oxide more than a kind,
The interpolation element that is selected from Cr, Al and Y that this Ni alloy powder contains 10～60 quality %,And Cr is that 10 quality % are above, Al is that 10 quality % are above, Y is more than 0.3 quality %, andAnd surplus is Ni and unescapable impurity.
6. a manufacture method for resistance film, is characterized in that, adopts claimed in claim 5The sputtering target that manufacture method obtains forms film by sputtering method on insulating materials substrate, by instituteThe film in atmosphere or in non-active gas environment obtaining, heat-treat 1 at 200～500 DEG C～10 hours.
7. the manufacture method of resistance film as claimed in claim 6, is characterized in that, spatters as above-mentionedThe method of penetrating is to adopt DC sputtering.
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