CN102117670A - Resistor material, sputtering target for forming resistive thin film, resistive thin film, thin film resistor and method of producing the same - Google Patents
Resistor material, sputtering target for forming resistive thin film, resistive thin film, thin film resistor and method of producing the same Download PDFInfo
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- CN102117670A CN102117670A CN2010105292597A CN201010529259A CN102117670A CN 102117670 A CN102117670 A CN 102117670A CN 2010105292597 A CN2010105292597 A CN 2010105292597A CN 201010529259 A CN201010529259 A CN 201010529259A CN 102117670 A CN102117670 A CN 102117670A
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Abstract
The aim of the invention is to provide a thin film resistor, a resistor material for manufacturing the thin film resistor and a method of producing the same. The resistivity, resistance-temperature characteristic, high-temperature stability and haloduric aquosity of the thin film resistor are excellent even after being treated at a relatively low temperature. According to the resistor material, 3 to 20 mass percentages of silicate glass is added in a Ni alloy. The Ni alloy contains 10 to 60 mass percentages more than one additional elements selected from Cr, Al and Y, and the remainders are Ni and unavoided impurities. SiO2 is the main component of the silicate glass. Meanwhile, the silicate glass comprises 0 to 90 mass percentages more than one component selected from B, Mg, Ca, Ba, Al , Zr and their oxides.
Description
Technical field
The present invention relates to as the thin film resistor of electronic unit and be used to obtain the resistance film of this thin film resistor, the sputtering target that this resistance film forms usefulness, the resistive element material that forms this sputtering target, further, also relate to their manufacture method.
Background technology
Use the thin film resistor of resistance film, be applied to chip resister, precision resistor, network resistor, high voltage resistor constant resistance device; Temperature detecting resistance body, temperature-sensitive resistor equitemperature transducer; And in the electronic unit of hybrid integrated circuit and composite module goods thereof etc.
For thin film resistor, require to have 4 characteristics: the absolute value of (1) temperature coefficient of resistance (TCR) is near 0 resistance-temperature characteristic; When (2) high temperature keeps through the time resistance change rate little high-temperature stability; (3) to the corrosion resistance (resistance to salt water) of people's sweat or seawater etc.; (4) resistivity height.
Be accompanied by the propelling of the miniaturization of electric and electronic goods, expecting thin film resistor is carried out miniaturization, but at the miniaturization of this thin film resistor, the resistivity that needs to keep above-mentioned characteristic and further improve the resistive element material that constitutes resistance film.
In thin film resistor, in most cases, as the resistive element material that is used to form resistance film, mainly having adopted Ta alloy, TaN compound, Ni-Cr is alloy etc.
Wherein, having used Ni-Cr is the resistance film of alloy, possess the ohm property (ohmic characteristics) that has as metallic character, the characteristics that variation is little and thermal stability is high that resistance value takes place with respect to variation of ambient temperature, therefore, be applied to thin film resistor usually.But, Ni-Cr be alloy as the resistive element material, have the low problem of resistivity.
Therefore, the someone has proposed a kind of resistance film, and it is that Ta, Al, Mo are made an addition to Ni-Cr is in the alloy, to improve resistivity (with reference to patent documentation 1).By this Ni-Cr that is added with Ta, Al, Mo is the resistance film that alloy obtains, with in the past use Ni-Cr is that the resistance film of alloy is compared, excellent corrosion resistance, but, dissolving starting voltage in the electrolytic corrosion test that adopts acid synthetic perspiration (JIS L0848) is less than 6V, therefore, expect to have the better resistance film of corrosion resistance.
In addition, this Ni-Cr is an alloy, imposes heat treatment for the characteristic that obtains to stipulate, by the desirable characteristics requirement to heat-treat greater than 500 ℃ high temperature.Therefore, need further to reduce described heat treatment temperature.
The 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 it carries out under the heat treated situation of resistance film with lower temperature, also can keep with the above-mentioned Ni-Cr that is added with Ta, Al, Mo be alloy phase with high resistivity, good resistance-temperature characteristic, high-temperature stability, and have highly corrosion resistant.
Resistive element material of the present invention, it is characterized in that, in the Ni alloy, the silicate that is added with 3～20 quality % is glass, wherein, this Ni alloy contains the interpolation element more than a kind among Cr, Al and the Y of being selected from of 10～60 quality %, and surplus is Ni and unescapable impurity, and this silicate is that glass is with SiO
2(silicon dioxide) is main component, and contain 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 usefulness, be to obtain: silicate glass frit end is mixed with the Ni alloy powder so that silicate glass frit end is the mode of 3～20 quality % by following manner, make the mixed-powder that is obtained be shaped to required shape, and make the formed body that is obtained in vacuum or non-active gas environment, with 50kg/cm
2Above adding depressed, and carries out sintering with 500～1400 ℃, and wherein, this silicate glass frit end is with SiO
2Be 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, this Ni alloy powder contains the interpolation element more than a kind among Cr, Al and the Y of being selected from of 10～60 quality %, and surplus is Ni and unescapable impurity.
The composition of this kind sputtering target comes down to identical with above-mentioned resistive element material.
Resistance film of the present invention adopts above-mentioned sputtering target, forms film by sputtering method on the insulating material substrate, with the film that obtained in atmosphere or in the non-active gas environment, heat-treats with 200～500 ℃ and to obtain in 1～10 hour.
The composition of this kind resistance film is also identical in fact with the resistive element material that constitutes above-mentioned sputtering target.
Resistance film of the present invention has following characteristic: resistivity is 300～1500 μ Ω Gm, temperature coefficient of resistance is in-25～+ scope of 25ppm/ ℃, 155 ℃ of high temperature keep in 1000 hours through the time resistance change rate be below 0.1%, and adopting the dissolving starting voltage in the electrolytic corrosion test of acid synthetic perspiration (JIS L0848) is more than the 9V.
Thin film resistor of the present invention, it is characterized in that, be to be made of insulating material substrate, the electrode that forms in the resistance film that forms on this insulating material substrate, the both sides of this resistance film on this insulating material substrate, 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 and obtain resistance film, use the thin film resistor of this resistance film, can realize the high resistivity of 300～1500 μ Ω cm simultaneously, the absolute value of temperature coefficient of resistance is in ± the good resistance-temperature characteristic of 25ppm/ ℃ scope, 155 ℃ of high temperature keep in 1000 hours through the time resistance change rate be higher high-temperature stability below 0.1%, and to adopt the dissolving starting voltage in the electrolytic corrosion test of acid synthetic perspiration (JIS L0848) be the above highly corrosion resistant (resistance to salt water) of 9V.
Also be, according to the present invention, can be with high resistance, electronic unit that high-temperature stability is good, be applied to excellent corrosion resistance than more having in the past under the harsh and unforgiving environments of requirement, and above-mentioned characteristic can the heat treatment of temperature obtains to be lower than in the past, therefore, the present invention also helps the manufacturing cost degradation that makes thin film resistor.
Description of drawings
Fig. 1 is the synoptic diagram of the thin film resistor that is suitable for of the present invention.
Fig. 2 is the synoptic diagram of expression electrolytic corrosion test.
The explanation of Reference numeral
1 insulating properties substrate (aluminum oxide substrate)
2 resistance films
3 electrodes (Au electrode)
4 drops
Embodiment
Thin film resistor requires that so-called high resistance is arranged, stable 4 characteristics of resistance-temperature characteristic, excellent high-temperature stability and highly corrosion resistant (resistance to salt water), is that alloy is that various trials have been carried out at the center in order to improve described characteristic with Ni-Cr.
At Ni-Cr is that the Ni-Cr that is added with Ta, Al and Mo in the alloy is an alloy, and the alloy phase ratio with is in the past still keeping original resistance-temperature characteristic and high-temperature stability, and tries to achieve the improvement to resistance and corrosion resistance.But, say as above-mentioned institute, obtain this specific character (particularly will make temperature coefficient of resistance be in the scope of regulation), above-mentioned resistive element material need be adopted and the film of film forming was heat-treated 1～10 hour with 200～600 ℃ temperature, according to desirable characteristics, need heat-treat with higher temperature (high temperature temperature on one side), in the hope of keeping or further improve above-mentioned characteristic, be the resistive element material that to heat-treat with lower temperature (low temperature temperature on one side) but more people expected.
The inventor etc. by the result who studies intensively repeatedly are: do not adopt the resistive element material that in the past is applied to the electronic component-use thin film resistor, interpolation silicate is glass in the Ni alloy and just measure in accordance with regulations, thus, can relatively reduce the heat treatment temperature that is used to obtain desirable characteristics, and, can further improve above-mentioned characteristic (particularly corrosion resistance).According to above-mentioned result of study, the inventor etc. have finished the present invention.
Resistive element material of the present invention, it is characterized in that: in the Ni alloy, the silicate that is added with 3～20 quality % is glass, wherein, this Ni alloy contains the interpolation element more than a kind among Cr, Al and the Y of being selected from of 10～60 quality %, and surplus is Ni and unescapable impurity, and this silicate is that glass is with SiO
2(silicon dioxide) is main component, and contain 0～90 quality % be selected from B, Mg, Ca, Ba, Al, Zr and their oxide more than a kind.
This resistive element material is to have a resistive element material that is characterized as feature that is had with above-mentioned composition, and it is so long as have identical in fact composition and get final product, to not restriction of mode.Therefore, the term of the resistive element material among the present invention, be in the process that resistance film forms from raw material to the resistance film till the general designation done of all modes.
The Ni alloy is from having constituted resistive element material of the present invention basically.This Ni alloy contains the interpolation element more than a kind among Cr, Al and the Y of being selected from of 10～60 quality %, and surplus is Ni and unescapable impurity.
Add element and have the reduction that various effects: Cr helps the absolute value of temperature coefficient of resistance, Al helps the raising of corrosion resistance, and Y helps the adhering raising of Ni alloy and glass powder.These add element, only add requirement according to desired characteristic, but for the characteristic in the thin film resistor that possesses the present application, are preferably and contain all interpolation elements.In order to bring into play various characteristics, need contain Cr respectively is that 10 quality % are above, Al is that 10 quality % are above, Y is more than the 0.3 quality %, and, it is counted more than the 10 quality % by total amount.When the addition that adds element was counted situation less than 10 quality % by total amount under, the resistivity of resulting resistance film can not become enough greatly.On the other hand, when these add elements when too much, can cause the bad stability after film forming, the heating, therefore the reproducibility variation, need be set at by below the total amount 60 quality %.From the viewpoint of the absolute value that reduces temperature coefficient of resistance, be preferably set to the scope that the total amount of adding element is in 40～50 quality %.Temperature coefficient of resistance, both the composition based on glass described later changed, and also the composition based on the Ni alloy changes.Consider that from this point preferably the interpolation element total amount to the Ni alloy is 40～50 quality %.
Resistive element material of the present invention is characterized in that, in this Ni alloy, the silicate that is added with 3～20 quality % is glass, and this silicate is that glass is with SiO
2(silicon dioxide) is main component, contain 0～90 quality % be selected from B, Mg, Ca, Ba, Al, Zr and their oxide more than a kind.
Silicate is glass, mainly is the effect with the resistance value that improves resistance film.In addition, improve the effect of the corrosion resistance of resistance film in addition.Further, be glass by containing silicate, can reduce relatively in order to obtain the heat treatment temperature that the film after the film forming is carried out of required characteristic.
Silicate is that glass is insulator, therefore, even there is the above a small amount of interpolation of 3 quality % also can obtain its effect.On the contrary,, can not come film forming, therefore have the problem of cost aspect by means of the DC sputter when addition can become insulator during greater than 20 quality %.In addition, silicate is the addition of glass, is preferably the scope of 5～10 quality %.
At silicate is in the glass, as additive, contain be selected from B, Mg, Ca, Ba, Al, Zr and their oxide more than a kind.Wherein, the content of these additives is set at below the 90 quality %.When the content of this additive during greater than 90 quality %, can cause the absolute value of temperature coefficient of resistance not to be in ± scope of 25ppm/ ℃ within.
By adding these B, Mg, Ca, Ba, Al, Zr or their oxide, can carry out the fusion temperature of resistance film, the fine setting of resistance to water.In addition, by Al or aluminium oxide (Al
2O
3) interpolation, the phase-splitting that can suppress resistance film takes place.But the present invention is not subjected to the influence of these additives, and above-mentioned only is to be that the additive that can contain in the glass gives example to silicate, and the silicate that does not contain these additives fully is that glass also can be applicable to the present invention.In addition, from the crystalline viewpoint of silicate glass, under the situation of adding this additive, be preferably and comprise whole B, Mg, Ca, Ba, Al, Zr.In addition, from same reason, comprise that also they are situations of oxide, and wish that its total amount is set at the scope of 30～70 quality %.
Sometimes expectation after sintering is carried out in hot pressing described later, is adjusted these additives and addition, so that silicate is non-crystallizableization of glass as required.Its reason is, when silicate was glass generation crystallization, the density that can cause the resistive element material does not rise and intensity reduces, and when carrying out film forming by sputter, can go wrong.
Next, the making that resistance film of the present invention is formed with sputtering target describes.Used silicate glass frit end and Ni alloy powder in the raw material of this sputtering target, wherein, described silicate glass frit end is with SiO
2Be 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, described Ni alloy powder contains the interpolation element more than a kind among Cr, Al and the Y of being selected from of 30～60 quality % (being preferably 40～50 quality %), 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, is preferably within the scope that is in 30～150 μ m, is more preferably the spherical atomized powder about 100 μ m.In addition, as silicate glass frit end, preferably using average grain diameter is 0.5～50 μ m, is preferably within the scope that is in 1～30 μ m, is more preferably the powder about 10 μ m.
From making the angle of material powder sintering, wish to be the thin material powder of particle diameter usually.But, when carrying out sintering, be not limited to this by hot pressing.Its reason is, when hot pressing, be filled with material powder in the carbonaceous mould, but there is the gap in the joint in the carbonaceous mould, and therefore, when material powder was meticulous, material powder can spill from the gap, has reduced machinability.
On the other hand, when the average grain diameter of Ni alloy powder is greater than 200 μ m, perhaps the average grain diameter at silicate glass frit end is under the situation greater than 50 μ m, the problem that target density reduces to take place.
These raw material are carried out dry type to be mixed, so that above-mentioned silicate glass frit end is 3～20 quality % (being preferably 5～10 quality %), acquisition is as the mixed-powder of material powder, the mixed-powder that is obtained is shaped to required shape, the formed body that is obtained is preferably made its sintering with pressure sintering, thus, can obtain above-mentioned sputtering target.As concrete sintering condition, preferably in vacuum or non-active gas environment, at 50kg/cm
2Above adding depressed, and 500～1400 ℃ of roastings 1～5 hour, makes it sintering thus.In the pressure sintering in this specification, also comprise HIP (waiting quiet hot pressing) method.When pressurizeing less than 50kg/cm
2, roasting time is less than under 1 hour the situation, can not obtain highdensity target.On the other hand, even surpass 5 hours hot pressing, can not obtain further to improve the effect of density.
For sintering temperature, wish softening point height than glass powder, and lower than the fusing point of Ni alloy.So the sintered body that obtains is prepared size dimension as required, waits by joint (bonding) to obtain sputtering target.
Then, the making to resistance film of the present invention describes.Use the sputtering target that obtains by as mentioned above, when carrying out film forming by sputtering method, acquisition and resistive element material be the film of same composition in fact.As the substrate of this moment, hope is Al
2O
3, SiO
2Deng insulator substrate.In addition, except sputtering method, also can be evaporation sheet (タ Block レ Star ト) with resistive element materials processing of the present invention, make the resistance film film forming by vapour deposition methods such as vacuum evaporations.
For sputtering method, be not subjected to the restriction of its kind, but, preferably adopt the DC sputter from the viewpoint of cost aspect with the property produced in batches.Though sputtering condition also is provided with according to sputter equipment, but, for example, the size that adopts target is that sputtering target, the power output of φ 75mm * 3mm is under the situation of sputter equipment of 200W (fixing), at voltage is that 400～600V, electric current are that 0.3～0.5A, Ar flow are that 15～25SCCM, total pressure are that 0.4～0.6Pa, TS distance (distance from the target to the substrate) is under the condition of 85mm, carries out film forming.
For the film that only carries out spatter film forming, temperature coefficient of resistance becomes big negative value, and then the resistance stability in high temperature is insufficient.Therefore, form, need heat-treat 1～10 hour at 200～500 ℃ in atmosphere or in the non-active gas according to the film after the film forming.By this heat treatment, the absolute value that can obtain temperature coefficient of resistance is the resistance film less than ± 25ppm/ ℃.
When heat treatment temperature during, the temperature coefficient of resistance instability of resulting resistance film less than 200 ℃, on the other hand, when heat treated temperature during greater than 500 ℃, the temperature coefficient of resistance of resistance film become big on the occasion of.In addition, when heat treatment time less than 1 hour situation under, the temperature coefficient of resistance instability of resulting resistance film, on the other hand, when heat treatment time greater than 10 hours situation under, do not see the effect of improving that further increase temperature coefficient of resistance stability is arranged yet, but strengthened cost for this reason.
In addition, in the composition of resistive element material of the present invention, this heat treatment temperature is that the situation of the resistance film of alloy is compared with having used the Ni-Cr that is added with Ta, Al and Mo, reduces relatively.Particularly, at this Ni-Cr is under the situation of alloy, according to composition, sometimes need under greater than 500 ℃ high temperature, heat-treat for obtaining desirable characteristics, but aspect the composition of resistive element material of the present invention, can become below 500 ℃ and can make heat treatment temperature in the whole compositing range move to lower 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 to adopt the dissolving starting voltage in the electrolytic corrosion test of acid synthetic perspiration (JISL0848) is the above better effect of 9V.
Thin film resistor of the present invention as shown in Figure 1, is to be made of insulating material substrate (1), resistance film (2) formed thereon and the electrode (3) that is formed at resistance film (2) both sides on the insulating material substrate (1).As electrode (3), except that the Au electrode, also can use electrodes such as Al, Ag, Cu, Ni, Cr.This thin film resistor has the characteristic that resistance film according to the present invention has.
Embodiment
As the Ni alloy powder, the average grain diameter that has prepared by total amount 40 quality % interpolation Cr, Al and Y (Cr: Al: Y=29.5: 10.0: 0.5 (mass ratio)) is the Ni alloy powder of 100 μ m.On the other hand, as silicate glass frit end, the average grain diameter that has prepared by total amount 50 quality % interpolation B, Mg, Ca, Ba, Al and Zr (B: Mg: Ca: Ba: Zr: Al=2: 5: 18: 18: 5: 2 (mass ratio)) is the SiO of 10 μ m
2Powder.
With these 2 kinds of powder and to make the addition at silicate glass frit end be 5 quality %, form material powder.
This material powder is packed in the carbonaceous mould of required form, adopt and extensively build the atmosphere hot pressing furnace (AHP) that Co., Ltd. (the Wide Building of Co., Ltd.) makes and carry out hot pressing.In the non-active gas environment that Ar flows with 2L/min, at so-called 200kg/cm
2Pressure, 1100 ℃ sintering temperature, 3 hours the condition of roasting time under, make this formed body sintering and obtain sintered body.
Adopt surface grinding machine (PSG-105DX, Co., Ltd. this work mechanism of ridge is made manufacturing) sintered body that obtained of processing and make thickness be 3.0mm after, adopt wire cutting machine tool (ワ イ ヤ one カ Star ト, AQ750L, the manufacturing of the ソ デ イ of Co., Ltd. Star Network) processing and make diameter is 75.0mm, then, use and to contain the indium scolder and buck plate (Bucking Plate) and sintered body are bonded together and form sputtering target.
To be installed on the DC sputter equipment (CFS-4ES, sesame Pu メ カ ト ロ ニ Network ス Co., Ltd. makes) as the above-mentioned sputtering target that obtains, and make TS distance (distance from the target to the substrate), be vented to 5 * 10 for 85mm
-4After the pa, importing purity is the Ar gas more than 99.999%, remains in the pressure of 0.5Pa, is that 200W, voltage are that 500V, electric current are that 0.4A carries out sputter so that thickness is 100nm with the sputtering power, and film forming is the film of 20mm * 25mm size on substrate.The substrate of this moment has used Al
2O
3
At the two ends of acquisition film, adopt same DC sputtering method to carry out the Au electrode that film forming is thickness 500nm.Then, in atmospheric environment, heat-treated 3 hours, obtain to use the thin film resistor that resistance film of the present invention is arranged with 300 ℃ temperature.
About the thin film resistor that is obtained, carried out the evaluation of resistivity described as follows, resistance-temperature characteristic, high-temperature stability and corrosion resistance (resistance to salt water).
About resistivity, be by adopting resistrivity meter (ロ レ ス タ GP MCP-T610 type, the ア of Mitsubishi Chemical of Co., Ltd. Na リ Star Network is made), detect with four-point probe method at room temperature and obtain.Among the present invention, will have resistivity is that the above thin film resistor of 300 μ Ω cm is judged as good merchantable brand.
About resistance-temperature characteristic, be that the thin film resistor that is obtained is inserted in the constant temperature mortise, to (the unit: Ω) adopt above-mentioned resistrivity meter to detect, calculate temperature coefficient of resistance, estimate thus of the resistance value in 25 ℃ and 125 ℃ by the resistance value that is obtained.Among the present invention, temperature coefficient of resistance is in ± thin film resistor in the 25ppm/ ℃ scope is judged as good merchantable brand.
About high-temperature stability, be that the thin film resistor that will be obtained kept 1000 hours in 155 ℃ thermostat, adopt above-mentioned resistrivity meter to detect the resistance value (unit: Ω), calculate resistance change rate (155 ℃, 1000 hours), estimate thus of its front and back by the resistance value that is obtained.Among the present invention, placing resistance value before the thermostat, be that thin film resistor below 0.1% is judged as good merchantable brand with the resistance value ratio after inserting as benchmark.
About resistance to salt water, be that the thin film resistor that is obtained is carried out following electrolytic corrosion test, detect the dissolving starting voltage, estimate thus.
At first, adopt digital multimeter (デ ジ タ Le マ Le チ メ one タ) (VOAC7521A, rock Tong Meter Measuring Co., Ltd. (the logical Co., Ltd. of measuring of rock) makes), detect according to the initial stage resistance value of four-end method to resistance film (2).Then, as shown in Figure 2, drip the acid synthetic perspiration (JIS L0848) of 30 μ L with micro syringe in the central authorities of resistance film (2), from the diameter of drop (4) and the length between the Au electrode (3), adjusting the voltage (Vp) between the Au electrode (3), is 1V so that be carried on the voltage (Vd) at drop (4) two ends.Voltage (Vp) between the Au electrode (3) is made as necessarily, after 3 minutes, washes and drying,, detect the resistance change rate of voltage loads front and back according to the four-end method detection resistance value at load voltage.
Adjust the voltage (Vp) between the Au electrode (3) and carry out above-mentioned detection repeatedly so that the voltage (Vd) that is carried on drop (4) two ends rises with the amplitude of 0.2V from 1V, thus, obtaining resistance change rate is greater than the voltage (Vd) of 0.2% o'clock drop (4) the two ends institute load dissolving starting voltage as resistance film (2).
Therefore, resulting dissolving starting voltage is the minimum value in the voltage at the drop two ends detected when satisfying following condition: with certain voltage, to load voltage between the Au electrode that drips two ends, acid synthetic perspiration (JIS L0848) back 3 minutes, wash with drying after, the resistance change rate of detection is greater than 0.2%.In the present invention, be that thin film resistor more than the 9.0V is judged as good merchantable brand with the dissolving starting voltage.
Except the addition that makes silicate glass frit end is 3 quality %, carry out similarly to Example 1 and obtain thin film resistor, its characteristic is detected.
Except the addition that makes silicate glass frit end is 10 quality %, carry out similarly to Example 1 and obtain thin film resistor, its characteristic is detected.
Except the addition that makes silicate glass frit end is 20 quality %, carry out similarly to Example 1 and obtain thin film resistor, its characteristic is detected.
Embodiment 5
Except in silicate glass frit end, not adding additive (content of the additive in the silicate glass frit end is 0 quality %), carry out similarly to Example 1 and obtain thin film resistor, its characteristic is detected.
Embodiment 6
The content of the additive in making silicate glass frit end is the 30 quality %, carries out similarly to Example 1 and obtains thin film resistor, and its characteristic is detected.
Embodiment 7
The content of the additive in making silicate glass frit end is the 70 quality %, carries out similarly to Example 1 and obtains thin film resistor, and its characteristic is detected.
Embodiment 8
The content of the additive in making silicate glass frit end is the 90 quality %, carries out similarly to Example 1 and obtains thin film resistor, and its characteristic is detected.
Embodiment 9
The content of the interpolation element in making the Ni alloy is the 10 quality %, carries out similarly to Example 1 and obtains thin film resistor, and its characteristic is detected.
Embodiment 10
The content of the interpolation element in making the Ni alloy is the 30 quality %, carries out similarly to Example 1 and obtains thin film resistor, and its characteristic is detected.
Embodiment 11
The content of the interpolation element in making the Ni alloy is the 50 quality %, carries out similarly to Example 1 and obtains thin film resistor, and its characteristic is detected.
Embodiment 12
The content of the interpolation element in making the Ni alloy is the 60 quality %, carries out similarly to Example 1 and obtains thin film resistor, and its characteristic is detected.
Comparative example 1
Except not adding silicate glass frit end, carry out similarly to Example 1 and obtain thin film resistor, its characteristic is detected.The resistivity of the thin film resistor of comparative example 1 be less than 300 μ Ω cm, resistance change rate for greater than 0.1%, and the dissolving starting voltage is very low.Understand thus, under the low relatively situation of the heat treatment temperature when obtaining resistance film, can not obtain to possess the thin film resistor of sufficient characteristic.
Comparative example 2
Except the addition that makes silicate glass frit end is 30 quality %, carry out similarly to Example 1, obtain sputtering target.But, when plan adopting this sputtering target to carry out the film forming of resistance film similarly to Example 1, because the conductivity of target is insufficient, so do not have can film forming.
Comparative example 3
The content of the additive in making silicate glass frit end is that 95 quality % and the addition of setting silicate glass frit end are the 10 quality %, carries out similarly to Example 1 and obtains thin film resistor, and its characteristic is detected.For the thin film resistor of comparative example 3, temperature coefficient of resistance surpasses ± scope of 25ppm/ ℃, dissolve starting voltage in addition for less than 9V, to understand thus, it can not reach resistance-temperature characteristic of the presently claimed invention and corrosion resistance.
Comparative example 4
The content of the interpolation element in making the Ni alloy is the 0 quality %, carries out similarly to Example 1 and obtains thin film resistor, and its characteristic is detected.For the thin film resistor of comparative example 4, resistivity is less than 300 μ Ω cm, and temperature coefficient of resistance is for surpassing ± scope of 25ppm/ ℃, and the dissolving starting voltage is less than 9V, understand thus, it can not reach resistance of the presently claimed invention, resistance-temperature characteristic, corrosion resistance.
Comparative example 5
The content of the interpolation element in making the Ni alloy is the 70 quality %, carries out similarly to Example 1 and obtains thin film resistor, and its characteristic is detected.For the thin film resistor of comparative example 5, temperature coefficient of resistance is for surpassing ± scope of 25ppm/ ℃, and the dissolving starting voltage be less than 9v, understanding thus, and it can not reach resistance-temperature characteristic of the presently claimed invention and corrosion resistance.
Various compositions among each embodiment, DC sputter could, the testing result of the film heat treatment temperature after the film forming and the thin film resistor characteristic that obtained, be shown in table 1 respectively.
Table 1
Embodiment 13
(Mg: Ca: Ba: Zr: Al=5: 20: 18: 5: average grain diameter 2 (mass ratioes)) is the SiO of 10 μ m except being added with Mg, Ca, Ba, Al and Zr as the employing of the end of the silicate glass frit in the material powder by total amount 50 quality %
2Beyond the powder, carry out similarly to Example 1 and obtain thin film resistor, its characteristic is detected.
Embodiment 14
Except the addition that makes silicate glass frit end is 7 quality %, carry out similarly to Example 13 and obtain thin film resistor, its characteristic is detected.
Embodiment 15
Except the addition that makes silicate glass frit end is 10 quality %, carry out similarly to Example 13 and obtain thin film resistor, its characteristic is detected.
Embodiment 16
Except in silicate glass frit end, not adding additive (content of the additive in the silicate glass frit end is 0 quality %), carry out similarly to Example 13 and obtain thin film resistor, its characteristic is detected.
Embodiment 17
The content of the additive in making silicate glass frit end is the 90 quality %, carries out similarly to Example 13 and obtains thin film resistor, and its characteristic is detected.
Embodiment 18
The content of the interpolation element in making the Ni alloy is the 50 quality %, carries out similarly to Example 13 and obtains thin film resistor, and its characteristic is detected.
Comparative example 6
Except not adding silicate glass frit end, carry out similarly to Example 13 and obtain thin film resistor, its characteristic is detected.
Comparative example 7
Except the addition that makes silicate glass frit end is 30 quality %, carry out similarly to Example 13 and obtain thin film resistor, its characteristic is detected.
Comparative example 8
The content of the additive in making silicate glass frit end is that 95 quality % and the addition of setting silicate glass frit end are the 10 quality %, carries out similarly to Example 13 and obtains thin film resistor, and its characteristic is detected.
Comparative example 9
The content of the interpolation element in making the Ni alloy is the 0 quality %, carries out similarly to Example 13 and obtains thin film resistor, and its characteristic is detected.
Comparative example 10
The content of the interpolation element in making the Ni alloy is the 70 quality %, carries out similarly to Example 13 and obtains thin film resistor, and its characteristic is detected.
In comparative example 6～10, also can see the trend same with comparative example 1～5.
Various compositions among each embodiment, DC sputter could, the testing result of the film heat treatment temperature after the film forming and the thin film resistor characteristic that obtained, be shown in table 2 respectively.
Table 2
Claims (7)
1. a resistive element material is characterized in that, in the Ni alloy, the silicate that is added with 3～20 quality % is glass,
This Ni alloy contains the interpolation element more than a kind among Cr, Al and the Y of being selected from of 10～60 quality %, and surplus is Ni and unescapable impurity,
This silicate is that glass is with SiO
2For main component and contain 0～90 quality % be selected from B, Mg, Ca, Ba, Al, Zr and their oxide more than a kind.
2. a resistance, diaphragm forms and uses sputtering target, it is characterized in that in the Ni alloy, the silicate that is added with 3～20 quality % is glass,
This Ni alloy contains the interpolation element more than a kind among Cr, Al and the Y of being selected from of 10～60 quality %, and surplus is Ni and unescapable impurity,
This silicate is that glass is with SiO
2For main component and contain 0～90 quality % be selected from B, Mg, Ca, Ba, Al, Zr and their oxide more than a kind.
3. a resistance film is characterized in that, in the Ni alloy, the silicate that is added with 3～20 quality % is glass,
This Ni alloy contains the interpolation element more than a kind among Cr, Al and the Y of being selected from of 10～60 quality %, and surplus is Ni and unescapable impurity,
This silicate is that glass is with SiO
2For main component and contain 0～90 quality % be selected from B, 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 resistance is in-25～+ scope of 25ppm/ ℃, 155 ℃ of high temperature keep in 1000 hours through the time resistance change rate be below 0.1%, and employing is more than the 9V according to the dissolving starting voltage in the acid synthetic perspiration's of JIS L0848 standard the electrolytic corrosion test.
4. a thin film resistor is characterized in that, it is made of insulating material substrate, the electrode that forms in the both sides of described resistance film of claim 3 that forms on this insulating material substrate and this resistance film on this insulating material substrate.
5. a resistance film forms the manufacture method of using sputtering target, it is characterized in that, so that silicate glass frit end is the mode of 3～20 quality % silicate glass frit end is mixed with the Ni alloy powder, make the mixed-powder that is obtained be shaped to required form, and make the formed body that is obtained in vacuum or non-active gas environment, at 50kg/cm
2Above adding depressed, and carries out sintering at 500～1400 ℃,
Wherein, this silicate glass frit end is with SiO
2For 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,
This Ni alloy powder contains the interpolation element more than a kind among Cr, Al and the Y of being selected from of 10～60 quality %, and surplus is Ni and unescapable impurity.
6. the manufacture method of a resistance film, it is characterized in that, adopt the described sputtering target of claim 5, on the insulating material substrate, form film by sputtering method, the film that obtained in atmosphere or in the non-active gas environment, was heat-treated 1～10 hour at 200～500 ℃.
7. the manufacture method of resistance film as claimed in claim 6 is characterized in that, is to adopt dc sputtering as above-mentioned sputtering method.
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