CN100540723C - Method for producing silicon oxide thin film and optical multilayer film - Google Patents
Method for producing silicon oxide thin film and optical multilayer filmDownload PDFInfo
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- CN100540723C CN100540723CCNB2004800109526ACN200480010952ACN100540723CCN 100540723 CCN100540723 CCN 100540723CCN B2004800109526 ACNB2004800109526 ACN B2004800109526ACN 200480010952 ACN200480010952 ACN 200480010952ACN 100540723 CCN100540723 CCN 100540723C
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Abstract
Translated fromChinese
Description
Technical field
The present invention relates to the method making the method for silicon oxide film and use this thin film fabrication optical multilayer.
Technical background
Silicon oxide film can be used for various application, as low refractive index film.Silicon oxide film can pass through depositions such as vacuum vapor deposition method, coating method.Yet glass, automotive glass, cathode ray tube (CRT) or flat pannel display that application examples is used as being applied in buildings adopt sputtering method under many situations, and this method is adapted at carrying out on the large-area substrates thin film deposition.
Usually in oxygen-containing atmosphere, utilize the Si target by under the deposition techniques silicon oxide film situation, know that if the power invariability that applies, voltage changes with the oxygen gas flow rate that joins in the atmosphere.Figure 3 shows that in the atmosphere that contains argon and oxygen when coming the cvd silicon oxide film voltage and add an example of relation (voltage change curve) between the oxygen gas flow rate in the atmosphere with the sputter of Si target.Fig. 3 is that oxygen gas flow rate is increased to the 80sccm state from the 0sccm state in the atmosphere, and the argon gas flow velocity in the atmosphere is held constant at the 125sccm state simultaneously, and oxygen gas flow rate is reduced under the 0sccm state afterwards, an example that obtains.
As shown in Figure 3, if the oxygen gas flow rate when improving sputter, in the initial period, it is constant that voltage remains essentially in high value.Yet voltage descends when oxygen gas flow rate reaches certain level, if oxygen gas flow rate further improves, voltage remains on substantially than low value.On the contrary, if oxygen gas flow rate descends, in the initial period, voltage remains on substantially than low value, and when oxygen gas flow rate reached certain level, voltage rose, and further descends as oxygen gas flow rate, and voltage remains on high value substantially.And in voltage change zone (zone of transition), oxygen gas flow rate is different under increasing voltage condition and voltage decline situation.
At this, in the zone of oxygen gas flow rate less than zone of transition, sedimentation rate height, but obtainable silicon oxide film is tending towards opaque, and uptake factor is tending towards increasing, thus become defective, film that promptly can not deposit transparent.And in the zone of oxygen gas flow rate greater than zone of transition, the silicon oxide film of acquisition can be transparent, but the defective that exists is that sedimentation rate is low.On the other hand, in zone of transition, a strong point that can obtain transparent silicon oxide film with high deposition rate is arranged.
Yet in zone of transition, because hysteresis phenomenon, voltage and oxygen gas flow rate are not constant relationship, thereby are difficult to by voltage and oxygen gas flow rate discharge is controlled at steady state.
As the method for eliminating the influence that zone of transition lags behind, and the method that has proposed to control by various loop lines (for example, JP-A-5-78836, JP-A-10-8247, JP-A-11-29863).
Yet in these situations, the problem of existence is owing to external influence such as abnormal discharge (arcing) or measuring error, and it is wrong that control is likely, the silicon oxide film of formation is likely uneven.Especially when arcing takes place, therefore voltage can descend, and sedimentation rate descends, in addition, when oxygen gas flow rate also when increasing, the control of carrying out subsequently will be impossible.Under these situations, also need to carry out feedback control, the equipment of Shi Yonging also is expensive thus.
In addition, WO01/27345 (after this being called D1) discloses a kind of formation by sputtering method and contains SiO in oxygen-containing atmosphere2For the method for the film of main ingredient, for reaching the purpose that obtains transparent silicon oxide film with high deposition rate, use C and Si atomicity than the sputtering target that contains SiC and metallization Si as 0.5-0.95, target density is 2.75 * 103Kg/m3To 3.1 * 103Kg/m3
JP-A-2003-13216 (after this being called D2) discloses a kind of method that forms transparent film by the sputtering method that uses reactant gas, the method that does not have the transparent film of zone of transition hysteresis as formation, wherein, the mixture that use contains compound and/or contains at least two kinds of different elements in zone of transition is as target, and thin film-forming method changes between metal mode and compound pattern with the variation of reactant gas concentration in described zone of transition.
JP-A-2003-121605; JP-A-2003-121636 and Jp-A-2003-121639 disclose a kind of anti-reflective film, near infrared protective membrane and bandpass filter; be characterised in that and on substrate, alternately deposit low refractive index film and high refractive index film; wherein; low refractive index film adopts sputter; deposit as target with conductive silicon carbide, and high refractive index film adopts sputter, use conductive titanium oxide to deposit as target.
Yet, in the D1 disclosed method, adopt the DC sputtering method, carry out sputter at oxygen gas flow rate greater than the zone of zone of transition, and make sedimentation rate not high enough.
In addition, the result as the inventor studies the D1 disclosed method finds using Si target situation to lag behind in zone of transition probably.That is, the inventor finds, when adopting the D1 disclosed method, is difficult to by voltage discharge in the zone of transition is controlled at stability state, and is difficult in zone of transition and makes uniform thin film continuously.
In addition, study the result of D2 disclosed method as the inventor, find, only less at the sputtering target area and the power density that applies hour adopts the DC pulse not lag behind in zone of transition, and the deposit transparent film will be possible consistently.This will specifically describe below.
At first, the inventor finds, and is when using C and Si atomicity to compare target as the silicon carbide-containing of 0.5-0.95 and silicon, only less (particularly less than about 300cm at the sputtering target area2) time, it is possible using the constant transparent film that is formed on zone of transition and not have to lag behind of DC pulse, and can not the formation film on the larger area substrate.And when target area is identical,, power density more may lag behind when increasing (being that sedimentation rate improves) time.Therefore, only less, and the power density that applies is hour at the sputtering target area, use the DC pulse can constantly be deposited on transparent film possible that zone of transition not have hysteresis.
In the D2 disclosed method, the sputtering target of use contains silicon carbide and silicon, and wherein C is 1 with the atomicity ratio of Si.And in this case, similar phenomenon takes place be easy to imagine.
Usually, deposit film or increase thin film deposition area situation on than large area substrates is necessary to increase the sputtering target area, to increase productivity.D2 does not disclose the content of relevant sputtering target area, and is still as described above, through the inventor's research, is easy to expect in the D2 disclosed method, big (specifically at least about 300cm at the sputtering target area2), and cause hysteresis when applying probably than high power density.In addition, expect lessly and apply the less situation of power density at the sputtering target area easily, hysteresis may disappear, but the problem that exists is that sedimentation rate is low, maybe can not form transparent film.
In addition, also expect easily in the D2 disclosed method, the surfaceness of the film that obtains is tending towards bigger, in the optical multilayer situation that is used for wherein having deposited many laminar surfaces, and the bigger optical multilayer of total thickness is when being used for bandpass filter, and directly the loss meeting of transmitted light is bigger owing to form mist.
The conductive carbonized silicon target also can be used for forming anti-reflection film etc., as disclosed among JP-A-2003-101605, JP-a-2003-121636 and the JP-A-2003-121639.Yet the inventor finds, with such target, can make sedimentation rate lower.
Otherwise, in recent years, developed a kind of optical multilayer that possesses various optical characteristics, if can reflect the optical multilayer of the light of some specific wavelength, can be by the silicon oxide film of alternating deposit low-refraction and the transparent film such as the Nb of high refractive index2O5Film or Ta2O5Film makes.Such optical multilayer can make to hundreds of layer transparent film by which floor deposits, and still, even only exist in one deck as the defective of inhomogeneous part, just can not be used.Therefore, for making optical multilayer, press for a kind of method of development at the same terms energy and continuous repeated deposition uniform thin film in high deposition rate.
Therefore, an object of the present invention is to provide a kind of method of making silicon oxide film, thereby a kind of can have the transparent film of consistent optical constant such as specific refractory power, uptake factor etc. with high deposition rate continuously at the same terms with repeated deposition on large area substrates, and make the optical multilayer that possesses desired properties and can be used for various uses.
Summary of the invention
Through broad research, the inventor finds, in containing the atmosphere of oxidizing gas, use C and the sputtering target of Si atomicity ratio as 0.5-0.95 silicon carbide-containing and silicon, when carrying out sputter with the alternating-current of CF, when using the Si target or under the D1 disclosed method situation, the hysteresis that takes place or not basically usually, therefore, control the oxygen concentration of voltage and zone of transition easily.Based on these discoveries, finished the present invention.
That is, the invention provides following (1) to (16).
(1) a kind of method of making silicon oxide film, this method comprises: in containing the atmosphere of oxidizing gas, using C and Si atomicity than being the silicon carbide-containing of 0.5-0.95 and the sputtering target of silicon, is 1-1 with frequency, the alternating-current of 000kHz carries out the AC sputter, cvd silicon oxide film on a substrate.
(2) according to the method for the manufacturing silicon oxide film of above-mentioned (1), the described zone of transition that sputters at is carried out.
(3) according to the method for the manufacturing silicon oxide film of above-mentioned (1) or (2), the area of described sputtering target is 300 to 100,000cm2
(4) according to the method for each manufacturing silicon oxide film in above-mentioned (1)-(3), described chip area is 0.1 to 20.0m2
(5) according to the method for each manufacturing silicon oxide film in above-mentioned (1)-(4), the shape of described sputtering target is a column.
(6) according to the method for each manufacturing silicon oxide film in above-mentioned (1)-(5), described oxidizing gas is an oxygen, and oxygen level is 35-60 volume % in described atmosphere.
(7) according to the method for each manufacturing silicon oxide film in above-mentioned (1)-(6), the power density that is applied in the sputter on the described sputtering target is at least 5W/cm2
(8) according to the method for each manufacturing silicon oxide film in above-mentioned (1)-(7), sedimentation rate described in the sputter is 40nmm/min at least.
(9) according to the method for each manufacturing silicon oxide film in above-mentioned (1)-(8), in described silicon oxide film, be benchmark with whole film, SiO2Component accounts for 99 quality % at least.
(10) according to the method for each manufacturing silicon oxide film in above-mentioned (1)-(9), the uptake factor of described silicon oxide film is 1 * 10 to the maximum-3
(11) according to the method for each manufacturing silicon oxide film in above-mentioned (1)-(10), described silicon oxide film thickness is 5-1 μ m.
(12) a kind of method of making optical multilayer, this method comprises: form the multilayer film that comprises multilayer film on a substrate, described multilayer film comprise one deck silicon oxide film at least, and described silicon oxide film is to adopt the method for each manufacturing silicon oxide film in above-mentioned (1)-(11) sedimentary.
(13) according to the method for the manufacturing optical multilayer of above-mentioned (12), described optical multilayer comprises at least 20 layer films.
(14) according to the method for the manufacturing optical multilayer of above-mentioned (12) or (13), any film outside the silicon oxide film that comprises in the described multilayer film is Nb2O5Film, TiO2Film or Ta2O5Film.
(15) according to the method for each manufacturing optical multilayer in above-mentioned (12)-(14), described optical multilayer is 5% to the maximum in the absorption of whole visible region.
(16) according to the method for each manufacturing optical multilayer in above-mentioned (12)-(15), the application of described optical multilayer is anti-reflective film, dichroic mirror, ultraviolet/infrared filter or bandpass filter.
Description of drawings
Shown in Figure 1 is the graphic representation of relation (voltage change curve) between voltage and oxidizing gas flow velocity when carrying out the present invention and making the silicon oxide film method.
Voltage change curve when carrying out sputter among the embodiment of being 1 shown in Figure 2.
Shown in Figure 3 is voltage change curve when carrying out sputter in comparative example 1.
Shown in Figure 4 is voltage change curve when carrying out sputter in comparative example 2.
Shown in Figure 5 is voltage change curve when carrying out sputter in comparative example 3.
Shown in Figure 6 is voltage change curve when carrying out sputter in comparative example 4.
Shown in Figure 7 is absorption curve that adopt to make the optical multilayer that the method for optical multilayer makes in embodiment 3.
Shown in Figure 8 is in embodiment 4, and the method for employing manufacturing optical multilayer makes as the spectral-transmission favtor of the optical multilayer of ultraviolet ray/infrared filter and the figure of spectral reflectivity.
Shown in Figure 9 is inembodiment 5, and the method for employing manufacturing optical multilayer makes as the spectral-transmission favtor of the optical multilayer of ultraviolet ray/infrared filter and the figure of spectral reflectivity.
Shown in Figure 10 is voltage change curve when carrying out sputter in embodiment 6.
Implement best mode of the present invention
Below, will describe the present invention in detail.
The method that the present invention makes silicon oxide film comprises, using C and Si atomicity than being the silicon carbide-containing of 0.5-0.95 and the sputtering target of silicon, in containing the atmosphere of oxidizing gas, is 1-1 with frequency, the alternating-current of 000kHz carries out the AC sputter, cvd silicon oxide film on a substrate.
The sputtering target that uses among the present invention comprises silicon carbide (SiC) and silicon (Si).
In the sputtering target that the present invention uses, the atomicity of C and Si (summation of Si among Si among the SiC and the Si) is at least 0.5 than C/Si, better at least 0.7, and maximum 0.95 is 0.9 preferably to the maximum.If the atomicity of C/Si is than too little, Si will become main ingredient, be easy at Si granule boundary generation crackle, and sedimentation rate can be lower.On the other hand, than too big situation, sedimentation rate can be lower in the C/Si atomicity.
Particularly, compare than the situation that is 1 with the C/Si atomicity, when applying same electric power, sedimentation rate can be brought up to 1.5 times from 1.3 times.On the contrary, when sedimentation rate was identical, the electric power that applies was reduced to 1/1.3 times from 1/1.5.
D1 public use C/Si atomicity is than being the sputtering target of 0.5-0.95, and discloses by using this sputtering target to improve sedimentation rate.
Yet in the disclosed DC sputtering method of D1, when C/Si atomicity ratio is 1 situation, sedimentation rate has only improved about 20%.And among the present invention, be 1-1 with frequency, the alternating-current of 000kHz carries out the AC sputter, and it is very big that sedimentation rate improves, at least about 100%.
The sputtering target density that the present invention uses is preferably 2.75 * 103To 3.1 * 103Kg/m3If density in this scope, when C/Si atomicity ratio is 0.5-0.95, can be discharged under steady state, and improved sedimentation rate.
Resistivity, discharge stability and the thermal conductivity of the sputtering target that uses from the present invention consider, preferably exists Si to fill SiC particulate space and constitute external phase.
The thermal conductivity of the sputtering target that the present invention uses is preferably 100W/ (mk) at least.If thermal conductivity is too low, sputtering target may be locally heated high temperature, thereby the damage as crackle may take place.In addition, because the local heating of sputtering target, heated portion is easy to oxidation, and sedimentation rate is descended.The thermal conductivity of sputtering target is high more good more.But,, do not have difference to suppressing such local heating to action of high temperature even thermal conductivity surpasses 200W/ (mk).
For obtaining the main film that is made of the silicon oxide film of low-refraction, in the sputtering target that the present invention uses, based on sputtering target, impurity (component except that Si and C) total amount is better less than 1 quality %.
Discharge stability during from thin film deposition considers, the relative density (filling ratio) of the sputtering target that the present invention uses better at least 60%.
In addition, consider that from carrying out the AC sputter resistivity of the sputtering target that the present invention uses better maximum 0.5 Ω m is considered from discharge stability, is preferably 0.03 Ω m.
The area of the sputtering target that the present invention uses is preferably 300-100,000cm2, 500-100 more preferably, 000cm2Within this scope, can carry out thin film deposition at large-area substrate in the short period.
The manufacture method of the sputtering target that the present invention is used is not particularly limited.For example, can be according to following manufacturing.
In the SiC powder, add dispersion agent, tackiness agent (as organic tackiness agent) and water, stir subsequently, preparation SiC slurry.Then, pour this slurry into a gypsum mold, subsequently casting.With the cast article thorough drying, then, from mould, take out, make moulded product.
Castmethod is a kind of industrial available method, should be cheap, and high productivity can be provided, and can form the irregularly shaped product except that flat board or have the product on big surface.
In the above example, adopt castmethod to obtain moulded product.In addition, can adopt press forming method or extrusion molding.In addition, can suitably select for the shape of moulded product, as plate shape or cylindricality.
After making shaping prod, carry out drying as requested.In the situation that is obtained sintered compact by moulded product, moulded product is in vacuum or nonoxidizing atmosphere, and 1,450-2 carries out sintering under 300 ℃ of temperature, obtains sintered products.Sintering temperature is preferably 1,500-2, and 200 ℃, more preferably 1,600-1,800 ℃, thereby be formed on the required hole of impregnated with molten Si in the next step.
Then, in vacuum or non-oxide reduced atmosphere, 1,450-2,200 ℃, melt of si is impregnated in the moulded product or its sintered products of acquisition, be filled into Si in the hole of moulded product or sintered products, make sputtering target.For the steam output that suppresses Si promotes the dipping of Si simultaneously, temperature is preferably 1,500-2,200 ℃, more preferably 1,500-1,800 ℃.
Do not need the method for impregnated with molten Si under the sintering moulded product owing to omitted sintering step, its productivity is high.On the other hand, the advantage of moulded product method of impregnated with molten Si after oversintering obtains sintered products is that impurity can evaporate during sintering, thereby can obtain highly purified sputtering target.
The sputtering target that uses among the present invention is processed into predetermined size usually, and is bonded to metal backing liner plate (as indium) by matrix material, or passes through as anchor clamps, and for example clip is mechanically anchored on the electrode, uses then.
The sputtering target shape can be plane or cylindricality.Preferred cylindricality, because this shape can be used the sputtering method that adopts rotatable cylindrical cathode, this method will be described below.
The atmosphere of using among the present invention (sputter gas) contains oxidizing gas.Oxidizing gas can be, for example, and oxygen, ozone, carbonic acid gas, or their mixture (as the mixture of oxygen and ozone).
The atmosphere of using among the present invention is had no particular limits, as long as described atmosphere contains above-mentioned oxidizing gas.For example, can adopt the mixture of oxidizing gas and rare gas element.Rare gas element can be, for example, and helium, neon, argon, krypton or xenon.Consider preferred argon wherein from economic benefit and discharging efficiency.These gases can use separately, or are used in combination with two or more mixture wherein.
In these atmosphere, the gaseous mixture of preferred argon gas and oxygen especially preferably contains the gaseous mixture of 35-60 volume % oxygen.
The substrate that uses among the present invention is had no particular limits, can adopt substrate commonly used.For example, can be sheet glass (as quartz glass plate), plastic sheet or plastics film.Especially consider from intensity and transparency, preferably adopt sheet glass.
Consider that from intensity substrate thickness is preferably 0.3-20.0mm, is preferably 0.5-10mm.
Among the present invention, can be at area less than 0.1m2Little substrate on deposit film.Yet, consider to make full use of advantage of the present invention, though on large-area substrate also effective deposit film, the area of substrate is preferably 0.1-20.0m2, 0.1-10.0m more preferably2, be preferably 0.1-3.0m2In addition, method can effectively be made the substrate with small area silicon oxide film below adopting, a kind of on large-area substrate cvd silicon oxide film and method that the substrate made from big area silicon oxide film is cut, or will cut into undersized many substrates in advance and be fixed on substrate holder and so on, and with whole this substrate holder as large-area substrate is arranged, form the method for silicon oxide film thereon.
Among the present invention, adopting above-mentioned sputtering target, is 1-1 with frequency in above-mentioned atmosphere, and the alternating-current of 000kHz carries out sputter.The frequency of the alternating-current that adopts among the present invention is 1kHz at least, and better 10kHz at least is maximum 1,000kHz, better maximum 100kHz.If frequency is within this scope, discharge will be stable, and can form the film with consistent optical constant.If the high frequency that adopts as use in the RF sputtering method, the equipment such as the energy that need can be bigger and more expensive.
In addition, compare with the DC sputtering method that adopts the DC pulse, adopting 1-1, in the AC sputtering method of 000kHz frequency, (1) anode and negative electrode alternately change, and anode is cleaned all the time, thereby discharge instability (arcing) can take place hardly, (2) impedance variations that produces owing to the anode disappearance is very little, thereby discharging condition is over time very little, and (3) can obtain the little smooth film of surfaceness.
Among the present invention, sputter zone of transition is more fortunately carried out.If carry out sputter, can obtain transparent silicon oxide film with high deposition rate in zone of transition.
Among the present invention, " zone of transition " is defined as follows.
Shown in Figure 1 is to apply constant electric power, change the flow velocity of oxidizing gas in the atmosphere, simultaneously other gas flow rates except that oxidizing gas remain unchanged down when carrying out the present invention and making the silicon oxide film method in the atmosphere, concern the graphic representation of (voltage change curve) between voltage and oxidizing gas flow velocity.
Among Fig. 1, when the flow velocity of oxidizing gas when 0 improves, voltage descends, and when this flow velocity further improves, voltage become remain on constant substantially than low value.Then, when the oxidizing gas flow velocity descended, voltage began to rise, and when this flow velocity further improves, and voltage becomes that to remain on high value constant substantially.And, make in the method for silicon oxide film in the present invention, in theory, can not form hysteresis, but in the actually operating, slightly form hysteresis, as shown in Figure 1.
Among Fig. 1, be that 0 o'clock voltage is set at A with the oxidizing gas flow velocity.And the tangent line that voltage remains on the voltage change curve when constant substantially than low value is set at D, the tangent line of obliquity absolute value when maximum was set at C when the oxidizing gas flow velocity was descended.Voltage at the infall of tangent line C and tangent line D is set at B.At this moment, " zone of transition " definition is the zone of voltage from B to B+ (A-B) * 0.9.
Promptly, " zone of transition " refers to, applying constant electric power, change the flow velocity of oxidizing gas in the atmosphere, simultaneously other gas flow rates except that oxidizing gas remain unchanged down when carrying out the present invention and making the silicon oxide film method in the atmosphere, among the figure that concerns between voltage and oxidizing gas flow velocity, when B is voltage at tangent line C and tangent line D infall, tangent line C is the oxidizing gas flow velocity decline situation tangent line of gradient absolute value when maximum that have a down dip, tangent line D is the tangent line that voltage remains on the voltage change curve when constant substantially than low value, A is an oxidizing gas flow velocity when being 0 o'clock voltage, and then zone of transition is the zone of voltage from B to B+ (A-B) * 0.9.
When the electric power that is applied in sputter on the sputtering equipment, the power density on sputtering target (power that applies is divided by the surface area of the discharge face of target) is preferably 5W/cm at least2, 10W/cm at least more preferably2
Sedimentation rate is preferably 20nmm/min at least, more preferably 40nmm/min at least.
Make in the method for silicon oxide film in the present invention, carry out sputter by adopting aforesaid method, the Si component oxidized gas institute oxidation of SiC in the sputtering target and Si, thereby on above-mentioned substrate the cvd silicon oxide film.Herein, C component and the reacted of the SiC in the sputtering target change CO into2Or CO, they can for example be removed from system by vacuum pump.
The present invention makes in the method for silicon oxide film, does not form basically in zone of transition to lag behind.Therefore, can carry out sputter in the higher zone of transition of sedimentation rate, and needn't use the loop line, because do not lag behind basically in zone of transition.Therefore, there is not the problem of using under the situation of loop line in this method, out of contior problem when promptly arcing taking place, or the problem of equipment that need be expensive.
Therefore, employing the present invention makes the method for silicon oxide film, can be easily with high deposition rate successive sedimentation uniform thin film.
In addition, by using the cylindricality sputtering target, can use the sputtering method that adopts rotatable cylindrical cathode, this is preferred.Utilize so rotatable cylindrical cathode, will improve the utilising efficiency of target, and reduce material cost.In addition, can reduce the depositional area of accumulation of deposits, thereby reduce arcing and film defects, improve the rate of utilization of equipment's capacity.
Make the SiO of the silicon oxide film of silicon oxide film method gained by the present invention2Component based on whole film, is preferably at least 99 quality %.Silicon oxide film better is 1.50 to the maximum in the specific refractory power of 633nm wavelength, better is 1.48 to the maximum.
Silicon oxide film contains a small amount of preferably or is substantially free of the C component.Based on whole film, when the C amount is not more than 0.2 quality %, can obtain the silicon oxide film that has low-refraction and do not have photoabsorption basically.Therefore, the uptake factor of silicon oxide film is 1 * 10 preferably to the maximum-3, better be 5 * 10 to the maximum-5
Film thickness (film thickness of geometrical dimension) to silicon oxide film has no particular limits.But, to consider and use silicon oxide film as anti-reflective film, film thickness is preferably 5nm to 1 μ m, and especially as optical multilayer the time, film thickness is preferably 5-500nm.
The present invention makes method the application aspect is not particularly limited of silicon oxide film, can be used for making normally used silicon oxide film.For example, this method is fit to be used for making the optics with various optical characteristics.
In addition, one preferred embodiment is, the method that the present invention makes silicon oxide film is used to make the method for optical multilayer of the present invention, will be described below.
The method of making optical multilayer of the present invention is following method, be included in and deposit the optical multilayer that comprises many films on the substrate, described film comprises one deck silicon oxide film at least, and described silicon oxide film is by the method deposition of above-mentioned manufacturing silicon oxide film of the present invention.
The present invention makes the substrate that uses in the optical multilayer membrane method with top described identical.
Make in the method for optical multilayer in the present invention, optical multilayer is had no particular limits, so long as comprise many layer films of one deck silicon oxide film at least.Other films as outside the silicon oxide film that comprises in the optical multilayer for example have Nb2O5Film, TiO2Film or Ta2O5Film.Can adopt the such film of ordinary method manufacturing.For example, at Nb2O5The film situation can be passed through the AC sputter, and the method for using metal Nb target to carry out thin film deposition is possible.In addition, can adopt the method that is of little use.For example, at Nb2O5The film situation, by the AC sputter, the method for using niobium oxides (NbOX) target to carry out thin film deposition.The thickness of other films in the optical multilayer except that the oxidation silicon film is preferably 10-500nm.In the optical multilayer, preferably for example can be alternating deposit silicon oxide film and Nb2O5The optical multilayer of film, alternating deposit silicon oxide film and TiO2The optical multilayer of film or alternating deposit silicon oxide film and Ta2O5The optical multilayer of film.
Film quantity in the optical multilayer is had no particular limits, as long as many layers are arranged, still,, have 20 layers at least, preferably at least 40 layers and maximum 500 layers as preferred implementation.To such embodiment, an obtainable really advantage is the film that can have consistent optical constant such as specific refractory power, uptake factor etc. with the high deposition rate successive sedimentation.
Application to optical multilayer has no particular limits.But, anti-reflective film, dichroic mirror, ultraviolet ray/infrared filter, bandpass filter or high reverberator are for example arranged.From these application aims, (wavelength is 400-700nm to the absorption in whole visible region, and condition is that other films except that the oxidation silicon film that optical multilayer comprises are TiO2Film, wavelength region may is 420-700nm, because by TiO2Film absorption) better is 5% to the maximum.
Make the method for optical multilayer according to the present invention, can easily form silicon oxide film optical multilayer film with high deposition rate, described optical multilayer has consistent optical constant.
Embodiment
Below, with reference to embodiment the present invention is described in further detail.However, it should be understood that the present invention is not subjected to the restriction of these embodiment.
1-1. the manufacturing of silicon oxide film
Embodiment 1
For determining to adopt the AC sputtering method on sheet glass, to form the condition of silicon oxide film, use a kind of sputtering equipment to carry out following test.After providing Ar gas with constant flow rate, discharge under constant keeping applying electric power.With 10sccm/5min speed, oxygen gas flow rate is brought up to 160sccm from 0sccm, then, is reduced to 0sccm with 10sccm/5min speed.Measure voltage change during this period.Test conditions is as follows.
Sputtering target:
Planar target comprises silicon carbide (SiC) and silicon (Si) (silicon carbide (SiC): 80 volume %, silicon (Si): 20 volume %; The C/Si atomicity is than=0.8)
Density: 3.0 * 103Kg/m3(relative density: about 100%)
Resistivity: 1.2 * 10-3Ω m.
The thermal conductivity that adopts laser flash method to measure: 150W/ (mK)
In X-ray diffraction is analyzed, only observe the crystallization phases of SiC and Si, and observe and have Si, be filled in SiC particulate space, and find it is successive.
The metallic impurity amount that ICP (inductively coupled plasma atomic emission assay method) measures, total amount with target is a benchmark, Al is 0.01 quality %, Fe is 0.005 quality %, and Ti is 0.002 quality %, and Ca is 0.001 quality %, Mg is less than 0.001 quality %, V is 0.003 quality %, and Cr is less than 0.001 quality %, and Mn is that 0.002 quality % and Ni are less than 0.001 quality %.
Target area: 2,000cm2
The Ar gas of atmosphere: 125sccm and the O of 0-160sccm2Gas
Pressure between film stage: 1.7 * 10-3To 2.7 * 10-3HPa
Ac frequency: 29kHz
The electric power of AC power supplies: 12kW
Negative electrode AC power density: 6W/cm2
Comparative example 1
For determining to utilize the DC sputtering method that adopts the DC pulse, the condition of cvd silicon oxide film on sheet glass uses a kind of sputtering equipment to carry out following test.After supplying with Ar gas with constant flow rate, discharge under constant keeping applying electric power.With 10sccm/5min speed, oxygen gas flow rate is brought up to 80sccm from 0sccm, then, is reduced to 0sccm with 10sccm/5min speed.Measure voltage change during this period.Test conditions is as follows.
Sputtering target: plane polycrystalline Si target
Target area: 1,350cm2
The Ar gas of atmosphere: 125sccm and the O of 0-80sccm2Gas
Pressure during the thin film deposition: 1.7 * 10-3To 2.7 * 10-3HPa
DC pulse-repetition: 50kHz
The electric power of DC power supply: 3.5kW
DC power density: 2.6W/cm2
Comparative example 2
According to the mode cvd silicon oxide film identical with comparative example 1, difference is to use to comprise silicon carbide (SiC) and silicon (Si) (silicon carbide (SiC): 80 volume %, silicon (Si): 20 volume %; C/Si atomicity ratio=0.8) target is as sputtering target, and target area becomes 548cm2, the DC power density is changed into 3.6W/cm2, the oxygen gas flow rate maximum value is 100sccm, and measures the voltage change during the thin film deposition.
Comparative example 3
According to the mode cvd silicon oxide film identical with embodiment 1, difference is, uses the polycrystalline Si target as sputtering target, and the oxygen gas flow rate maximum value is changed into 90sccm, and the electric power of the AC energy is changed into 8kW, and negative electrode AC power density is 4W/cm2, the voltage change during the mensuration thin film deposition
Comparative example 4
According to the mode cvd silicon oxide film identical with comparative example 1, difference is a following conditions, measures the voltage change during the thin film deposition.
Sputtering target: planar target comprises silicon carbide (SiC) and silicon (Si) (silicon carbide (SiC): 80 volume %, silicon (Si): 20 volume %; The C/Si atomicity is than=0.8)
Target area: 140cm2
The Ar gas of atmosphere: 40sccm and 02 gas of 0-16sccm
The speed that oxygen gas flow rate improves and reduces: 1sccm/3min
Pressure between film stage: 1.3 * 10-3HPa
DC pulse-repetition: 40kHz
The electric power of DC power supply: 0.75kW
DC power density: 5.4W/cm2
Embodiment 2
Employing is used to comprise silicon carbide (SiC) and silicon (Si) (silicon carbide (SiC): 80 volume %, silicon (Si): 20 volume % at the AC of zone of transition sputtering method; C/Si atomicity ratio=0.8) planar target, 1,200mm * 1, deposit transparent silicon oxide film on the sheet glass of 500mm * 1mm (thickness).The condition of cvd silicon oxide film is as follows.
The condition of cvd silicon oxide film
Target area: 3,000cm2
The Ar gas of atmosphere: 270sccm and the O of 210sccm2Gas (O2Gas: 44 volume %)
Pressure between film stage: 3.19 * 10-3HPa
Ac frequency: 40kHz
The electric power of the AC energy: 39.1kW
Negative electrode AC power density: 10.3W/cm2
Cathodic electricity power: 31kW
Sedimentation rate: 40.5nmm/min
With total film is benchmark, SiO2Component concentration: 99.5 quality %
Uptake factor: 4.3 * 10-5
Comparative example 5
Utilize plane silicon carbide (SiC) target (silicon carbide (SiC); 100 volume %, the C/Si atomicity is than=1.00), the AC sputtering method of employing zone of transition, 1,200mm * 1, deposit transparent silicon oxide film on the sheet glass of 500mm * 1mm (thickness).Adjust mode of deposition, make sedimentation rate identical with embodiment 2.The condition of cvd silicon oxide film is as follows:
The condition of cvd silicon oxide film
Target area: 3,000cm2
The Ar gas of atmosphere: 200sccm and the O of 230sccm2Gas (O2Gas: 54 volume %)
Pressure between film stage: 2.49 * 10-3HPa
Ac frequency: 40kHz
The electric power of the AC energy: 76.7kW
Negative electrode AC power density: 14.8W/cm2
Cathodic electricity power: 44.5kW
Sedimentation rate: 40.5nmm/min
1-2. the voltage change curve during the sputter
The voltage change curve is shown in Fig. 2 to Fig. 6 respectively during the sputter of measuring among embodiment 1 and the comparative example 1-4.
As shown in Figure 2, make method (embodiment 1) situation of silicon oxide film in the present invention, discovery is on the voltage change curve during the thin film deposition, basically do not lag behind in zone of transition, even also discharge can be controlled at steady state in zone of transition, can be with the transparent silicon oxide film of the constant manufacturing of high deposition rate.
Yet, extremely shown in Figure 5 as Fig. 3, using direct current, the situation (comparative example 1) of using the Si target to carry out sputter is being used direct current (DC pulse), the target that use comprises silicon carbide and silicon carries out sputter situation (comparative example 2) and uses alternating-current, the situation (comparative example 3) of using the Si target to carry out sputter is found, all observes the hysteresis in zone of transition under each situation, and be difficult to control the discharge in the zone of transition, be difficult at the constant manufacturing silicon oxide film of zone of transition.
Therefore, clearly, the method for having only the present invention to make silicon oxide film can be carried out under the influence of the variety of issue that causes of not lagged behind.
In addition, as shown in Figure 6, even using direct current (DC pulse), the target that use comprises silicon carbide and silicon carries out the situation of sputter, if make target area and the power density that applies less, hysteresis may less (comparative example 4), but in situation with deposit film on the large-area substrate, or making the big situation of depositional area, must increase target area to boost productivity, especially in target area at least about 500cm2The time, observe hysteresis, as shown in Figure 4 (comparative example 2).
And, in the identical situation of target area, when power density increases (becoming big with sedimentation rate), form hysteresis probably.Therefore,, require to apply big power density, lag behind thereby form probably if attempt to improve sedimentation rate.
1-3. the relation between sputtering target and cathodic electricity power
To comparing between embodiment 2 and the comparative example 5, obviously, in comparative example 5, compare with embodiment 2, when sedimentation rate was identical, cathodic electricity power was 1.44 times of embodiment 2.
This means that when cathodic electricity power is identical sedimentation rate among the embodiment 2 is 1.44 times of comparative example 5.
Therefore, obviously, compare than the situation that is 1.00 with C/Si atomicity in the sputtering target, compare than the situation within the scope of the invention with the C/Si atomicity of sputtering target, sedimentation rate is obviously high.
2-1. manufacturing optical multilayer
Embodiment 3
Repeated using zone of transition AC sputtering method deposits Nb on 500mm * 200mm * 1.1mm (thickness) sheet glass2O5Film (film thickness: 10nm) and adopt zone of transition AC sputtering method thereon the cvd silicon oxide film (film thickness: operation 10nm) is formed on and has alternately deposited Nb on the glass substrate2O5The optical multilayer of film and silicon oxide film, total number of plies is 40 layers.Deposition Nb2O5The condition of film and silicon oxide film is as follows:
Deposition Nb2O5The condition of film
Sputtering target: metal Nb target
The Ar gas of atmosphere: 125sccm and the O of 80sccm2Gas
Pressure between film stage: 2.3 * 10-3HPa
Ac frequency: 26kHz
AC power supplies voltage: 277V
AC power supplies electric current: 48A
The electric power of AC power supplies: 12kW
Cathode voltage: 619V
Cathodic current: 24A
Sedimentation rate: 42nmm/min
The condition of cvd silicon oxide film
Sputtering target: planar target comprises silicon carbide (SiC) and silicon (Si) (silicon carbide (SiC): 80 volume %, silicon (Si): 20 volume %; The C/Si atomicity is than=0.8)
The Ar gas of atmosphere: 125sccm and the O of 135sccm2Gas (O2Gas: 52 volume %)
Pressure between film stage: 3.3 * 10-3HPa
Ac frequency: 29kHz
AC power supplies voltage: 439V
AC power supplies electric current: 50A
AC power supplies voltage: 20kW
Cathode voltage: 456V
Cathodic current: 49A
Sedimentation rate: 42nmm/min
Embodiment 4
Repeated using zone of transition AC sputtering method deposits Nb on 500mm * 250mm * 1.0mm (thickness) quartz glass plate2O5Film (film thickness: 10nm) and adopt zone of transition AC sputtering method thereon the cvd silicon oxide film (film thickness: operation 10nm), form optical multilayer, function is ultraviolet ray/infrared filter, alternately deposits Nb on glass substrate2O5Film and silicon oxide film, total number of plies is 50 layers.Deposition Nb2O5The condition of film and silicon oxide film is as follows:
Deposition Nb2O5The condition of film
Sputtering target: metal Nb target
Target area: 2,000cm2
The Ar gas of atmosphere: 125sccm and the O of 80sccm2Gas
Pressure between film stage: 2.2 * 10-3HPa
Ac frequency: 26kHz
AC power supplies voltage: 371V
AC power supplies electric current: 60A
AC power supplies voltage: 20kW
Cathode voltage: 890V
Cathodic current: 30A
Sedimentation rate: 21nmm/min
Form the condition of silicon oxide film
Sputtering target: planar target comprises silicon carbide (SiC) and silicon (Si) (silicon carbide (SiC): 80 volume %, silicon (Si): 20 volume %; The C/Si atomicity is than=0.8)
Target area: 2,000cm2
The Ar gas of atmosphere: 125sccm and the O of 135sccm2Gas
Pressure between film stage: 3.3 * 10-3HPa
Ac frequency: 29kHz
AC energy voltage: 439V
The electric current of DC energy: 50A
The electric power of the AC energy: 20kW
Cathode voltage: 456V
Cathodic current: 49A
Sedimentation rate: 42nmm/min
According to making the optical multilayer that function is ultraviolet ray/infrared filter with embodiment 4 identical modes, but deposition Nb2O5The condition of film is adjusted as follows.
Deposition Nb2O5The condition of film
Sputtering target: NbOx target
Target area: 2,000cm2
The Ar gas of atmosphere: 125sccm and 03 gas of 24sccm (corresponding at the zone of transition deposit film)
Pressure between film stage: 1.9 * 10-3HPa
Ac frequency: 27kHz
AC power supplies voltage: 381V
AC power supplies electric current: 62A
The electric power of AC power supplies: 21kW
Cathode voltage: 1,045V
Cathodic current: 39A
Sedimentation rate: 46nmm/min
Comparative example 6
Attempt according to making optical multilayer, but be to use the target of polycrystalline Si target, but be difficult to the control discharge, and can not obtain the optical multilayer that function is ultraviolet ray/infrared filter as the cvd silicon oxide film with embodiment 3 identical modes.
2-2. the absorption curve of optical multilayer
To the optical multilayer that embodiment 3 makes, be determined at the absorption of 300-800nm wavelength region.The absorption curve that obtains is shown in Fig. 7.
Among Fig. 7, be the absorption of sheet glass, obviously, be 2% to the maximum by the whole visible region of being absorbed in of optical multilayer, and be substantially zero in the absorption of maximum 400nm.That is, obviously,, can obtain transparent optical multilayer according to the method for manufacturing optical multilayer of the present invention.
2-3. the spectral-transmission favtor of ultraviolet ray/infrared filter and spectral reflectivity
The function thatembodiment 4 and 5 is made is the optical multilayer of ultraviolet ray/infrared filter, is determined at 300-1, the spectral-transmission favtor of 200nm wavelength region and spectral reflectivity.The results are shown in Fig. 8 and Fig. 9.
Clearly, by Fig. 8 and Fig. 9, to adopting the present invention to make ultraviolet ray/infrared filter that the optical multilayer membrane method makes, transmittance regional at the entire ultraviolet line and infrared spectral range is 5% to the maximum, and is shielded fully at the light of ultra-violet region and infrared spectral range.
3-1. make silicon oxide film with rotatable cylindrical cathode
Embodiment 6
For determining to adopt the AC sputtering method, the condition of cvd silicon oxide film on sheet glass is carried out following test with a kind of sputtering equipment.In sputtering equipment, be provided with two rotatable cylindrical cathodes and an AC power supplies that applies AC voltage.After providing Ar gas with 300sccm, discharge under the electric power constant (18kW) that keeps simultaneously applying.Reduce Ar gas and improve oxygen with 10sccm/5min speed, the overall flow rate that makes Ar gas and oxygen is 300sccm.The Ar gas velocity becomes 0sccm, and after oxygen gas flow rate becomes 300sccm, on the contrary, increases Ar gas with 10sccm/5min speed, reduces oxygen, makes that Ar gas and oxygen gas flow rate summation are 300sccm.
Test conditions is as follows.
Sputtering target:
Columnar target comprises silicon carbide (SiC) and silicon (Si) (silicon carbide (SiC): 80 volume %, silicon (Si): 20 volume %; The C/Si atomicity is than=0.8)
Density: 3.0 * 103Kg/m3(relative density: about 100%)
Resistivity: 1.2 * 10-3Ω m
Thermal conductivity by laser flash method mensuration: 150W/ (mK)
In X-ray diffraction is analyzed, only observe the crystallization phases of SiC and Si, and the Si that exists is filled in the intergranular space of SiC, and constitutes an external phase.
The metallic impurity amount that ICP (inductively coupled plasma atomic emission assay method) measures, Al is 0.01 quality %, Fe is 0.005 quality %, Ti is 0.002 quality %, and Ca is 0.001 quality %, and Mg is less than 0.001 quality %, V is 0.003 quality %, Cr is less than 0.001 quality %, and Mn is 0.002 quality %, and Ni is less than 0.001 quality %.
Target area: 3,580cm2
The Ar gas of atmosphere: 0-300sccm and the O of 0-300sccm2Gas
Pressure between film stage: 2.4 * 10-3To 3.7 * 10-3HPa
Ac frequency: 29-36kHz
The electric power of AC power supplies: 18kW
Columnar target speed of rotation: 10rpm
3-2. the voltage change curve during the sputter
Be shown in Figure 10 as the voltage change during the sputter of embodiment 6 mensuration.
As shown in figure 10, discovery is adopting rotatable cylindrical cathode to carry out the method situation (embodiment 6) that the present invention makes silicon oxide film, the zone of transition of the voltage change curve during thin film deposition is not observed hysteresis basically, even and in zone of transition, discharge can be controlled at steady state, can be with the transparent silicon oxide film of the constant manufacturing of high deposition rate.
Commercial Application
The method of silicon oxide film constructed in accordance can have consistent optics with the high deposition rate successive sedimentation The film of characteristic. And, make the method for optical multilayer according to the present invention, can be with high deposition rate easily Deposition has the optical multilayer of silicon oxide film, and described optical multilayer has consistent optical constant.
Claims (16)
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| US20020117785A1 (en)* | 1999-10-13 | 2002-08-29 | Asahi Glass Company Limited | Sputtering target, process for its production and film forming method |
| CN2516565Y (en)* | 2001-12-03 | 2002-10-16 | 深圳豪威真空光电子股份有限公司 | Device for preparing silica film by intemediate-frequency reactive magnet control sputtering |
| CN1397661A (en)* | 2001-06-26 | 2003-02-19 | 三井金属矿业株式会社 | Sputtering target for high resistance transparent conductive membrane and mfg. method of high resistance transparent conductive membrane |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20020117785A1 (en)* | 1999-10-13 | 2002-08-29 | Asahi Glass Company Limited | Sputtering target, process for its production and film forming method |
| CN1397661A (en)* | 2001-06-26 | 2003-02-19 | 三井金属矿业株式会社 | Sputtering target for high resistance transparent conductive membrane and mfg. method of high resistance transparent conductive membrane |
| CN2516565Y (en)* | 2001-12-03 | 2002-10-16 | 深圳豪威真空光电子股份有限公司 | Device for preparing silica film by intemediate-frequency reactive magnet control sputtering |
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| Mid frequency sputtering-a novel tool for large area coating. G.Brauer,et al.Surface and Coatings Technology,Vol.94-95. 1997* |
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