CN101427353A - Silicon etching method - Google Patents

Silicon etching method Download PDF

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CN101427353A
CN101427353A CNA2007800141949A CN200780014194A CN101427353A CN 101427353 A CN101427353 A CN 101427353A CN A2007800141949 A CNA2007800141949 A CN A2007800141949A CN 200780014194 A CN200780014194 A CN 200780014194A CN 101427353 A CN101427353 A CN 101427353A
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fluorine
gas
silicon
etching
water
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CN101427353B (en
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石井彻哉
中岛节男
大塚智弘
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Sekisui Chemical Co Ltd
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Sekisui Chemical Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • H01L21/3065—Plasma etching; Reactive-ion etching
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/32009—Arrangements for generation of plasma specially adapted for examination or treatment of objects, e.g. plasma sources
    • H01J37/32366—Localised processing

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  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
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Abstract

To improve the rate of etching of silicon. [MANS FOR SOLVING PROBLEMS] Water is added to CF4 (which is a fluorine-containing raw material containing fluorine and having no reactivity with silicon) in such an amount that a dew point of the resulting gas becomes 10 to 40 DEG C. The resulting low-dew-point fluorine-containing raw gas is passed through a plasma space (26) having a pressure close to the atmospheric pressure, thereby producing a fluorine-containing reactive gas containing COF4 (which is a non-radical fluorine-containing intermediate gas) and having a ratio between the number of fluorine atoms (F) and the number of hydrogen atoms (H) (i.e., (F)/(H) ratio) larger than 1.5. A reactive gas comprising O3 (which is an oxidizing gas capable of oxidizing silicon) and the fluorine-containing reactive gas produced in the plasma space (26) is sprayed onto a material to be treated at a temperature ranging from 10 to 50 DEG C. COF4 (which is a fluorine-containing intermediate gas) is reacted with water to produce a fluorine-containing etching gas capable of etching silicon oxide (e.g., HF).

Description

The engraving method of silicon
Technical field
The present invention relates to a kind of fluorine that uses is the method for the silicon of gas etch substrate surface.
Background technology
For example in patent documentation 1,2, record: utilizing the silicon of ozone oxidation wafer surface and become on the basis of silica (formula 1), using hydrofluoric acid (hydrofluoric acid) etching.Hydrofluoric acid makes its evaporation with the hydrofluoric acid vapor generator, and it is imported to wafer surface.In addition, chip temperature is recited as more than 50 ℃, is preferably more than 60 ℃.
Record in the patent documentation 3: by at CF 4In fluorine is to take place in the gas to discharge near the atmospheric pressure, generates HF, COF 2Deng, and then, make COF 2With at CF 4Deng in the water reaction that mixes, become HF (formula 2), utilize HF etching (formula 3) silica that obtains in this wise.
Si+2O 3→ SiO 2+ 2O 2(formula 1)
COF 2+ H 2O → CO 2+ 2HF (formula 2)
SiO 2+ 4HF+H 2O → SiF 4+ 3H 2O (formula 3)
In patent documentation 4, record: from the CF of humidification 4, utilize the atmos plasma discharge, obtain HF, to wherein adding O 3, etching oxidation silicon.
In patent documentation 5, record: make CF 4And O 2Atmosphere pressure discharging takes place, and the base that gains freedom from the plasma space, imports on the substrate of 20 ℃ of temperature or 100 ℃ the etching single crystal silicon with it.
In patent documentation 6, record: make humidification CF 4Or dry CF 4Atmosphere pressure discharging takes place, with 90 ℃ of substrate temperatures, etching silicon metal.
Patent documentation 1: the spy opens communique 2003-No. 264160
Patent documentation 2: the spy opens communique 2004-No. 55753
Patent documentation 3: the spy opens communique 2000-No. 58508
Patent documentation 4: the spy opens communique 2002-No. 270575
Patent documentation 5: the spy opens flat 04-No. 358076 communiques
Patent documentation 6: the spy opens communique 2000-No. 164559
Summary of the invention
The silicon etching in past not too can increase etching speed.The inventor considers following reason.
For example, in described patent documentation 1,2 etc., will from the beginning with the form of hydrofluoric acid, supply to the substrate that constitutes by wafer as the hydrofluoric acid of corrosive agent.Thereby, on substrate surface, except the oxidation reaction of following formula 1, the etching reaction of following formula 3 should only take place.In the reaction of this formula 3, silica is along with becoming volatile SiF 4, and regenerate water (H 2O).
At this, under the low situation of substrate temperature, the described water that regenerates condenses, and is added in the condensed phase (hydrofluoric acid of liquid phase) of the hydrofluoric acid on the substrate surface.So, along with the carrying out of etching reaction, the condensed phase growth, thickness increases.On the other hand, the necessary ozone of the oxidation of silicon is dissolved in condensed phase and spreads in condensed phase and then the arrival substrate surface, just can help the oxidation of silicon afterwards, if but the thickness of condensed phase increases the then ratio minimizing of ozone arrival substrate surface.Thereby the diffusion control speed of generation ozone causes the reduction of silicon oxidation speed in condensed phase.
In addition, the minimizing of the hydrogen fluoride concentration of condensed phase also may be a reason that underspeeds.
On the contrary, under the high situation of substrate temperature, though the problem of the growth of hydrofluoric acid condensed phase disappears, but then, as shown in Figure 4, the distribution coefficient between gas one liquid of ozone reduces.That is, temperature uprises more, and then ozone is difficult to be dissolved in the hydrofluoric acid condensed phase more.Thereby the dissolving control speed of generation ozone still causes the reduction of silicon oxidation speed.
Thereby substrate temperature exists makes silicon oxidation speed become the value at peak.Past is preferred substrate temperature about 60 ℃.As shown in Figure 4, near 60 ℃, distribution coefficient is about 0.1, can only dissolved ozone integral body about 1 one-tenth.But, owing to must suppress the growth of hydrofluoric acid condensed phase, thus 60 ℃ be the limiting temperature of lower limit, be difficult to make it to be lower than 60 ℃ and improve distribution coefficient.In addition, the hydrofluoric acid water of high concentration (hydrofluoric acid of liquid phase) since hydrofluoric acid than the easy evaporation of the water capacity, so if become high temperature, then hydrofluoric acid concentration self also reduces.
From such situation, in the silicon etching in the past,, can not become sufficient value even silicon oxidation speed is peak dot yet, naturally, etching speed also has to become insufficient big size.
In addition, as patent documentation 5 etc., using the free radical that generates with plasma to carry out under the etched situation, if too separate with the distance between the substrate in the plasma space, then free radical inactivation before arriving substrate causes that etching speed reduces.On the other hand, if make the distance between plasma space and the substrate too close, then plasma may wounded substrate.Thereby the degree of freedom of the setting range of the separating distance of plasma space and substrate is little.
But, utilizing the etching reaction of formula 3 to regenerate water is because fluorine such as HF are that etching gas has hydrogen atom.The inventor considers above, obtains following opinion, that is: exist hydrogen atom bring harmful effect also can for the silicon etching in etching gas.
The present invention just is being based on described opinion and is proposing, and it is the method that etching comprises the object being treated of silicon, it is characterized in that,
Execution is set in the jeting process that 10 ℃～50 ℃ object being treated sprays reactant gas to temperature,
Described reactant gas contains
(a) can make silicon oxidation oxidizing gas and
(b) thus contain and become with water reaction that can to carry out etched fluorine to silica be that the fluorine of the non-free radical of etching gas is an intermediate gas, number of fluorine atoms (F) is (F)/(H) with the ratio of number of hydrogen atoms (H)〉1.5 fluorine is reactant gas.
Thus, can be on the surface of object being treated, the generation fluorine is that the fluorine of intermediate gas and water is the reaction of formation of etching gas.This fluorine be etching gas and object being treated oxidation form silica generation etching reaction the time, even produced water, can be in the etching gas reaction of intermediate gas at new fluorine also with this water consumption.Thereby the cohesion of the water that takes place in the time of needn't preventing the etching reaction of silica even the object being treated temperature is 10 ℃～50 ℃ a low temperature, also can suppresses condensed phase and grow on the surface of object being treated.Utilize the low temperatureization of object being treated, can improve the solubility of oxidizing gas to condensed phase.Utilize the growth of condensed phase to suppress, can guarantee the extension of oxidizing gas in condensed phase.And, by making with fluorine is that intermediate gas is that the fluorine of main component is that the ratio of number of hydrogen atoms (H) and the number of fluorine atoms (F) of reactant gas becomes (F)/(H)〉1.5, can be reliably in fluorine is the etching gas reaction of intermediate gas, consume the water that in etching reaction, generates, can suppress the growth of condensed phase reliably.Thus, can further guarantee the extension of oxidizing gas in condensed phase fully.As a result, can improve silicon oxidation speed, and then, etching speed can be improved.
In addition, be intermediate gas by the fluorine that uses non-free radical, ejection portion that can corresponding reactant gas and the separating distance between the object being treated avoid taking place the reduction of etching speed or the damage of object being treated, can improve design freedoms such as distance setting.
In order to obtain initial fluorine is etching gas, also can be only initial what react, and be to add steam in the intermediate gas to fluorine.At object being treated be amorphous silicon situation etc. down, also can utilize the hydrogen and described oxidizing gas acquisition water that contain in this object being treated, utilizing this water and fluorine is intermediate gas, obtaining initial fluorine is etching gas.Perhaps, also can supply with initial fluorine to the object being treated surface be that other different fluorine of intermediate gas are etching gas, the water that utilizes this etching reaction to generate, and carrying out fluorine is the etching gasization of intermediate gas.
Thereby can utilize the evaporation waters such as temperature of object being treated to cut down the hydrofluoric acid condensed phase.In this case, preferably utilize the steam in etching reaction or supply gas to add to replenish the part water that evaporates.
Described fluorine is the ratio more preferably (F)/(H) of number of fluorine atoms (F) and the number of hydrogen atoms (H) of reactant gas〉3.Thus, can be further consume water (H2O) reliably, can further suppress the growth of condensed phase reliably.
It is described than (F)/(H) to utilize following (1)～(3) to measure.
(1) with fourier-transform infrared spectroscope (FTIR), the fluorine of measuring described fluorine and being in the reactant gas is the concentration of intermediate gas, tries to achieve fluorine and be the number of hydrogen atoms (H) in the intermediate gas.
(2) Ph of water (alkaline water) is measured on the limit, and limit logical a certain amount of described fluorine in this water is a reactant gas, from the variation of Ph, ask feed described fluorine be before the reactant gas with feed after the change in concentration Δ H of hydrogen.This change in concentration is that described fluorine is that the water and the HF reaction of formation of reactant gas causes.Asking described fluorine from this change in concentration Δ H is number of fluorine atoms (F) the reactant gas.
(3) utilize described (1) and (2), calculate (F)/(H).
Described fluorine be intermediate gas to be preferably the fluorine that does not contain hydrogen be molecule, for example be preferably COF 2, but be not limited to this, be that the gas of etching gas gets final product so long as generate fluorine such as HF with the water reaction, also can CF 3OH etc. contain the gas of hydrogen, also can be F 2
Described fluorine is that reactant gas is preferably as follows describedly and generates.
Not having reactive fluorine with silicon is to add dew point in the raw material to become 10 ℃～40 ℃ (water of the amount of steam partial pressure 1.2282kPa～7.3844kPa), obtaining low dew point fluorine is unstrpped gas.Feed near atmospheric pressure the plasma space low dew point fluorine to be unstrpped gas.
Thus, can obtain abundant containing with COF 2The fluorine that is the master is that the fluorine of intermediate gas is a reactant gas.In addition, can realize the facilitation operated.In addition, under the bigger situation of the input electric power of plasma discharge, preferably, also add oxygen except being to add in the raw material the water to fluorine.
At this, be meant the scope of 0.5bar～2bar near the atmospheric pressure, preferably in the scope of 0.9～1.1bar.
The preferred execution:
To fluorine-containing and with silicon do not have reactive fluorine be add in the raw material dew point become 10 ℃～40 ℃ (water of the amount of steam partial pressure 1.2282kPa～7.3844kPa), the water that to obtain low dew point fluorine be unstrpped gas adds operation;
The plasma operation that it is unstrpped gas that near atmospheric pressure plasma space feeds described low dew point fluorine; Spray the jeting process of the reactant gas of the gas contain the oxidizing gas that can make silicon oxidation and the described plasma operation of experience with the object being treated that is set in 10 ℃～50 ℃ to temperature.
Utilizing described plasma operation, can be that to obtain containing a lot of fluorine be that the fluorine of intermediate gas is the reactant gas composition to raw material from fluorine.
Described oxidizing gas is preferably ozone.Thus, oxidation constitutes the silicon of object being treated reliably.
Described oxidizing gas preferably utilizes aerating oxygen acquisition in ozonizer.Thus, can obtain ozone with high concentration as oxidizing gas.
The ozone addition is preferably many as much as possible.At fluorine is that intermediate gas is COF 2, fluorine is that etching gas is under the situation of HF, the interpolation flow of ozone at least must be at COF 2Volume flow and more than 1/2nd the summation size of the volume flow of HF, be preferably about its 2 times.
Described oxidizing gas can utilize also that aerating oxygen obtains near atmospheric pressure the plasma space.
This plasma space can be identical with the plasma space that to be used for the described low dew point fluorine of plasma be unstrpped gas, also can be different.Under the former (identical) situation, can shared 1 plasma creating device, can constitute by simplification device.Under latter's's (difference) the situation, can obtain oxidizing gas such as ozone with high concentration.In addition, can hang down the plasma that the dew point fluorine is a unstrpped gas effectively.
Also can carry out:
Mix that to contain fluorine and not have reactive fluorine with silicon be that raw material, content can make that dew point is that raw material is 10 ℃～40 ℃ (water and the oxygen of steam partial pressure 1.2282kPa～7.3844kPa) obtain the mixed processes of mist with respect to this fluorine; With
Make this mist by near the plasma space the atmospheric pressure, the plasma operation of reaction of formation gas thus; With
Be set in 10 ℃～50 ℃ object being treated to temperature and spray the jeting process of described reactant gas.
Thus, can be in 1 plasma space, from fluorine be unstrpped gas to obtain fluorine be intermediate gas, obtain oxidizing gas from oxygen.
The preferably described relatively fluorine of the ratio of the oxygen in the described mist is that raw material is 5～20vol%.By making lower limit become 5vol%, even the input electric power height of plasma discharge, also can generate fluorine fully is intermediate gas.Making the upper limit become 20vol% is because if surpass this upper limit, then fluorine is that the generation of intermediate gas is saturated.Described oxygen ratio is according to the input electric power of plasma discharge and difference is 7～13vol% but more preferably described relatively fluorine is a raw material.
Described fluorine is that raw material is preferably CF 4
Thus, in described plasma space, be intermediate gas as fluorine, can obtain COF 2, CF 3OH, F 2Deng.
In described plasma operation, the concentration of the water after the logical described plasma space be preferably before logical below 1/10.
Thus, can be to consume most water in the etching gas reaction of intermediate gas at fluorine, can suppress the growth of the condensed phase on object being treated surface reliably, can improve etching speed reliably.
Described dew point is preferably 10 ℃～30 ℃ (steam partial pressure 1.228kPa～4.2467kPa), more preferably 10 ℃～20 ℃ (steam partial pressure 1.228kPa～2.3392kPa) further is preferably 10 ℃～17 ℃ (steam partial pressure 1.2282kPa～1.9383kPa).
Thus, can improve etching speed reliably.
The temperature upper limit of described object being treated also can be lower than 50 ℃, also can be for below 40 ℃.
More preferably 10 ℃～30 ℃ of the temperature of described object being treated.
Thus, can make oxidizing gas such as ozone easily be dissolved in the condensed phase on object being treated surface, can improve silicon oxidation speed.Perhaps, thus can make hydrogen fluoride etc. become easily dissolving improves hydrofluoric acid concentration.Thereby, can further improve etching speed.
Making the temperature range lower limit of described object being treated become 10 ℃ is in order to prevent the dewfall to the object being treated surface.(be under 25 ℃ the situation in room temperature, relative humidity as long as 38% with interior.)
Also can replace 10 ℃, make the temperature range lower limit of described object being treated become indoor dew point.
Thus, indoor moisture can be prevented, the growth of the condensed phase on object being treated surface can be further improved reliably at the object being treated surface sweating.
The temperature of described object being treated is room temperature more preferably.
Thus, object being treated needn't be heated or cool off, the adjustment operation of object being treated can be omitted.
If utilize the present invention.Even water takes place when etching reaction, also this water can be used for the reaction of formation that fluorine is an etching gas.Thereby, even the object being treated temperature is a low temperature, also can suppresses condensed phase and on the object being treated surface, grow.Thus, can improve silicon oxidation speed, and then, etching speed can be improved.
Description of drawings
Fig. 1 is the summary construction diagram of the Etaching device in the 1st execution mode of the present invention.
Fig. 2 is the summary construction diagram of the Etaching device in the 2nd execution mode of the present invention.
Fig. 3 is that expression change substrate temperature detecting is raw material CF to fluorine relatively 4Result's the curve chart of embodiment 1 of etching speed of water addition (dew point demonstration).
Fig. 4 is the curve chart of gas-liquid distribution coefficient of the ozone of expression relative temperature.
Among the figure, 1-Etaching device, 2-substrate temperature governor motion, 3-conveying mechanism, 4-reactant gas feed system, 10-ozone supply system, 11-oxygen supply portion, 12-ozonizer, 13-ozone supply road, 20-fluorine are gas supply system, and 21-fluorine is a raw material supplying portion, 22-humidifier, 23-plasma head, 24-electrode, 25-power supply, 26-plasma space, 27-ejection road, 41-attraction road, 42-exhaust gear, 90-substrate, 91-silicon fiml (object being treated).
Embodiment
The 1st execution mode of the present invention below is described.
As shown in Figure 1, the film 91 (object being treated) of formation silicon on substrates such as glass 90.The silicon that constitutes film 91 can be amorphous silicon, also can be crystalline silicon such as many crystallizations of micro-crystallization Si Si.Also can be for silicon being the film that contains 0～20% left and right sides hydrogen of main component.Substrate 90 is made of silicon such as wafers, and himself also can become etch target (object being treated).Also can be n type or the P type silicon of mixed P (phosphorus) or B (boron) etc.Enumerate an example, in the substrate that in the TFT that liquid crystal is used, uses,, then, become the noncrystalline Si of the object being treated of present embodiment with the plasma CVD film forming at film forming SiN on glass.
In the drawings, the thickness of substrate 90 and silicon fiml 91 is shown by exaggerative.
Etaching device 1 possesses substrate temperature governor motion 2, conveying mechanism 3 and reactant gas feed system 4.
Substrate temperature governor motion 2 comprises heater or cooler (omitting diagram), and the temperature of substrate 90 that be processed is adjusted to set point of temperature.The temperature of substrate 90 is preferably 10 ℃～50 ℃, and more preferably 10 ℃～30 ℃, further more preferably room temperature.The temperature range lower limit also can replace 10 ℃ becomes indoor dew point.In that substrate temperature is become under the situation of room temperature, also can omit substrate temperature governor motion 2.
Conveying mechanism 3 for example relatively moves substrate 90 relative reactivity gas supply systems 4 to the left and right directions of Fig. 1.
Reactant gas feed system 4 possesses ozone supply system 10 and fluorine is a gas supply system 20.
Ozone supply system 10 comprises oxygen supply portion 11 and the ozonizer 12 that is connected with this oxygen supply portion 11.Detailed diagram is omitted, and oxygen supply portion 11 has oxygen cylinder or mass flow adjuster, supplies with the oxygen (O of regulation flow to ozonizer 12 2).Ozonizer 12 is from the ozone (O of oxygen generation as oxidizing gas 3).With to the oxygen ratio, be preferably 1～15vol% at the ozone concentration of the export department of ozonizer 12.
Fluorine be gas supply system 20 to possess fluorine be raw material supplying portion 21, be raw material supplying portion 21 humidifier 22 that is connected and the distance type plasma head 23 that is connected with this humidifier 22 with this fluorine.Detailed diagram is omitted, and fluorine is that to have savings be the CF of raw material as fluorine in raw material supplying portion 21 4Groove or mass flow adjuster, supply with the CF of regulation flows to humidifier 22 4 Humidifier 22 is to being the CF of raw material supplying portion 21 from fluorine 4Add the water of ormal weight in the gas.This water addition is preferably the CF after interpolation 4The dew point of gas becomes 10 ℃～40 ℃ amount, more preferably becomes 10 ℃～30 ℃ amount, further preferably becomes 10 ℃～20 ℃ amount.Thus, generate the ratio CF of lower dew point in the past 4Gas.
Distance type plasma head 23 is configured to utilize the top of the substrate 90 that described conveying mechanism 3 relatively moves.Plasma head 23 possesses pair of electrodes 24,24.Power supply 25 is connected with an electrode 24, another electrode 24 ground connection.Form slot-shaped space 26 24,24 of pair of electrodes.On the gas road of the upper end of this inter-electrode space 26 connection from humidifier 22.Opposite face at electrode is provided with solid dielectric.
To electrode 24 service voltages, in inter-electrode space 26, form Atomospheric pressure glow discharge from power supply 25 thus.Thus, inter-electrode space 26 becomes the atmos plasma space.
Service voltage is preferably Vpp=10～15kV.Voltage waveform can be interrupted waes such as pulse, also can be continuous waves such as sine wave.
Extend from the bottom of the inter-electrode space 26 of distance type plasma head 23 on short ejection road 27, and the bottom on this ejection road 27 is in the lower aperture of plasma head 23.Pars intermedia on ejection road 27 is collaborated from the ozone supply road 13 of ozonizer 12.Near the lower ending opening (ejiction opening) on the ejection road 27 below plasma head 23, attract open-ended (attract mouthful) on road 41 with the direction configured separate that relatively moves of substrate 90.Attract mouthfuls 41 to be connected with exhaust gear 42 such as vacuum pump.
Utilize described Etaching device 1, the method for the silicon fiml 91 of etching substrates 90 is described.
Substrate temperature is regulated operation
Utilize substrate temperature governor motion 2, the substrate 90 that will handle is adjusted to 10 ℃～50 ℃, is preferably 10 ℃～30 ℃ set point of temperature.Set point of temperature at substrate 90 is under the situation of room temperature, needn't regulate temperature especially.
This substrate 90 is disposed at the downside of plasma head 23.
The ozonisation operation
Then, with the oxygen of ozonizer 12 ozonisation from oxygen supply portion 11.Thus, obtain oxygen ozoniferous.Derive this oxygen ozoniferous to ozone supply road 13.
Water adds operation
In addition, importing from fluorine in humidifier 22 is the CF of raw material supplying portion 21 4In humidifier 22, adding dew point becomes 10 ℃～40 ℃, preferably becomes the water of 10 ℃～30 ℃ amount.This adds water yield in plasma operation described later, preferably in plasma space 26 by after the concentration of water be the amount below 1/10 before passing through.
The plasma operation
In the inter-electrode space 26 of plasma head 23, import water and add CF afterwards 4Parallel, from power supply 25 to electrode 24 service voltages.Thus, in inter-electrode space 26, begin Atomospheric pressure glow discharge, make inter-electrode space 26 become the plasma space.Thus, CF 4By plasma, react with the water that adds, generate COF 2, CF 3OH, F 2Be intermediate gas or be HF of etching gas etc. as fluorine in fluorine.And, by setting described water addition, COF 2Generate more than HF etc. intermediate gas.Thus, can derive that intermediate gas are rich (for example to be rich in COF to ejection road 27 2) fluorine be reactant gas.
In addition, under the bigger situation of the input electric power of plasma discharge, except to CF 4The middle interpolation beyond the water, preference is as also adding relative CF 4Be the oxygen (O about 10vol% 2).Thus, can generate more reliably as fluorine is the COF of intermediate gas 2
Mixed processes
Is rich in COF described 2Gas in, mix oxygen ozoniferous from ozone supply road 13.Utilize this mist to constitute " containing the reactant gas that oxidizing gas and fluorine are intermediate gas ".
Jeting process
From these mists of ejection road 27 ejection, to the jet surface of the silicon fiml 91 of substrate 90.Thus, on the surface of silicon fiml 91, react, carry out the etching of silicon fiml 91.The COF relevant with reaction 2, HF, O 3Deng being non-free radical, can corresponding plasma head 23 and the operating distance of 90 of substrates, avoid the reduction of etching speed or the damage of substrate 90, setting that can facilitation head height degree etc. can improve the degree of freedom of design.
With the gas that attracts road 41 to suck after handling, discharge with exhaust gear 42.And then, with conveying mechanism 3 substrate 90 is relatively moved, etch processes substrate 90 integral body.
The etched detailed mechanism of this silicon is still uncertain, and reaction as follows may take place.Ignore from the HF in the supply gas in plasma space 26.
[situation 1]
(oxidizing process)
Si+2O 3→ SiO 2+ 2O 2(formula 11)
(HF generative process)
2COF 2+ 2H 2O → 2CO 2+ 4HF (formula 12)
(HF course of dissolution)
4HF+4HF+4H 2O → 4HF 2 -+ 4H 3O +(formula 13)
(etching process)
SiO 2+ 4HF 2 -+ 4H 3O +→ SiF 4+ 2H 2O+4H 2O+4HF (formula 14)
As shown in Equation 13, on the surface of silicon fiml 91, form the film of the condensed phase (hydrofluoric acid of liquid phase) of hydrofluoric acid.Contact each composition in the described ejection gas on the surface of this condensed phase.
If then dissolve in condensed phase according to the ratio of the distribution coefficient (Fig. 4) of relative substrate temperature on the ozone in ejection gas contact condensed phase surface.Substrate temperature waits low temperature owing to being configured to 10 ℃～50 ℃, so distribution coefficient is big, can increase the solubility of ozone in condensed phase fully.In addition,, decompose, can make ozone life-span long enough so can prevent ozone owing to be low temperature.The ozone that dissolves in condensed phase spreads in condensed phase, arrives the surface of silicon fiml 91.Silicon by this ozone oxidation formation silicon fiml 91 becomes silica (formula 11).Because ozone solubility is big, so can increase silicon oxidation speed fully.
Contact constitutes the hydrofluoric acid of condensed phase on the silica that obtains in this wise, and silica becomes volatile SiF 4, be attracted, remove (formula 14) from attracting mouth.Like this, carry out the silicon etching.Because silicon oxidation speed is big, so can increase etching speed fully.
Utilize described etching reaction to generate water (steam) (formula 14).The part of this water (2H that the right of formula 14 is the 2nd 2O) with described ejection gas in COF 2Reaction generates HF (formula 12).Thereby, this water (2H 2O) in 2 reactions of formula 12 and formula 14, move as the catalyst.In addition, utilize the nubbin (4H that the right of formula 14 is the 3rd of the water of described etching reaction generation 2O) be used to the formation (the 3rd on the left side of formula 13) of hydrofluoric acid condensed phase, and then in the etching reaction of silica, be consumed (formula 14).
Thus, can prevent or suppress the lip-deep condensed phase growth of base material.Thereby, can prevent the diffusion control speed of the ozone in condensed phase, can make ozone diffuse to the surface of silicon fiml 91 reliably.Thereby, can improve with the solubility of described ozone in condensed phase and work mutually, further increase the oxidation rate of silicon fiml 91.
In addition, can prevent diffusion control speed, etching reaction is carried out reliably for hydrofluoric acid.
And then, utilize the growth of condensed phase to suppress, can make the SiF that in etching reaction, takes place 2Discharge apace from substrate 90 surfaces, can prevent SiO 2Separate out again.As a result, can further improve etching speed.
In formula 12, from COF 2The HF that produces dissolves (the 1st on the left side of formula 13) in the hydrofluoric acid condensed phase, can help the etching (formula 14) of silica.HF (the 4th on the right of formula 14) for utilizing etching reaction to generate is dissolved on (the 2nd on the left side of formula 13) in the hydrofluoric acid condensed phase too, helps the etching (formula 14) of silica
Formula 11～formula 14 can be generalized into following reaction equation.
Si+2O 3+ 2COF 2→ SiF 4+ 2O 2+ 2CO 2(formula 15)
In theory, if the initial supply H that is handling only 2Intermediate gas COF then takes place in O 2HFization reaction (formula 12), be the beginning with it, the chain reaction of carrying out formula 11～14, integral body is carried out the reaction by formula 15 expression.Thereby, as long as reaction is Once you begin, afterwards, even from the COF that is rich in plasma space 26 2Supply gas in do not contain HF fully, as long as contain the COF of intermediate gas 2, just can continue silicon etch process.
At this, in the composition that in supply gas, contains from plasma space 26, if considering fluorine is that etching gas and fluorine are the number of hydrogen atoms (H) of intermediate gas and hydration integral body together and the ratio (F)/(H) of number of fluorine atoms (F), then in formula 15, number of fluorine atoms (F) is 2COF relatively 2In 4, hydrogen atom (H) is 0, so (F)/(H)=infinity.
On the other hand, in the etching reaction of generating polynomial 14, must on the surface of silicon fiml 91, there be the condensed phase of thickness to a certain degree, the result, if condensed phase is thin excessively, then evaporation simply owing to evaporation of water.In addition, the water that in etching reaction, produces (the 2nd on the right of formula 14) also can with COF 2Meet and then HFization reaction (formula 12) takes place before and SiF 4Deng mouthful attracting from attracting together.Therefore, in fact, preferably carry out described water continuously and add operation.
Under for the situation of usually among the TFT (thin-film transistor) that liquid crystal drive is used, using, in film, contain about 10% the hydrogen of having an appointment with the amorphous silicon of plasma CVD making.In this case, shown in 11a, utilize the oxidation reaction of ozone to generate water.Can utilize this water that initial HFization reaction (formula 12) takes place, the water after perhaps carrying out replenishes.
SiH 2x+ (2+x) O 3→ SiO 2 +(2+x) O 2+ xH 2O (formula 11a)
At this, SiH 2xBe illustrated in 1 silicon atom of object being treated and contain 2x hydrogen atom, in amorphous silicon,
Figure A200780014194D0015191438QIETU
, silicon is 2x=0 usually.
Consider that the W-response formula under the situation that contains hydrogen of object being treated is as follows.
SiH 2x+ (2+x) O 3+ 2COF 2→ SiF 4+ (2+x) O 2+ 2CO 2(formula 15a)
Described situation 1 is to be conceived to COF specially in the supply gas composition from plasma space 26 2Consider to react, but in supply gas, also can contain some HF.Considering under the situation of HF, each reaction of formula 11～formula 14 can rewritten as described below.
[situation 2]
(oxidizing process)
Si+2O 3→ SiO 2+ 2O 2(formula 11b)
(HF generative process)
COF 2+ H 2O → CO 2+ 2HF (formula 12b)
(HF course of dissolution)
2HF+4HF+2HF+4H 2O → 4HF 2 -+ 4H 3O +(formula 13b)
(etching process)
SiO 2+ 4HF 2 -+ 4H 3O +→ SiF 4+ H 2O+4H 2O+H 2O+4HF (formula 14b)
The 2HF correspondence that the left side of formula 13b is the 1st is from the HF in the supply gas in plasma space 26.HF in this supply gas dissolves to the hydrofluoric acid condensed phase from the hydrofluoric acid condensed phase on the surface of silicon fiml 91 and the interface of air layer.In addition, the HF that the 4HF correspondence that the left side of cotype 13b is the 2nd generates in etching reaction (the 5th on the right of formula 14b), the COF in the corresponding supply gas of the 2HF that the left side of formula 13b is the 3rd 2The HF that in the HFization reaction, generates (the 2nd on the right of formula 12b).
In addition, the H that in etching reaction (formula 14b), generates 2Part among the O (the 2nd on the right of formula 14b) is at COF 2HFization reaction (the 2nd on the left side of formula 12b) in use other parts (the 3rd on the right of formula 14b) use in the new etching reaction (formula 14b) in experience HF dissolving (the 4th on the left side of formula 13b) back.
The reaction of formula 11b～14b is with H 2O is the chain reaction that the positive feedback of media plays effect.This chain reaction can be passed through at the range regulation substrate temperature below 50 ℃, thus the H on increase and decrease silicon fiml surface 2The amount of O is controlled.Because the water addition that described water adds in the operation is few, so the H on silicon fiml surface 2The O amount is also few, and the silicon fiml surface often demonstrates dried trend.Thereby, utilize the adjustment below 50 ℃, can control the H on silicon fiml surface fully 2The O amount, and then, the growth of condensed phase can be suppressed reliably.In addition, because the H on silicon fiml surface 2The a small amount of easily evaporation of O amount is so correspondingly generate H redundantly because of the HF in the supply gas 2O (the 4th on the right of formula 14b) thus, can guarantee the H on silicon fiml surface 2The O amount is kept reaction.
In addition, by in supply gas, there being HF, can when handling beginning, obtain being used for HFization COF reliably 2H 2O.
Conclusion formula 11b～14b is shown below.
Si+2O 3+ COF 2+ 2HF → SiF 4+ 2O 2+ CO 2+ H 2O (formula 15b)
In formula 15b, the number of hydrogen atoms (H) that helps to react is 2 among the 2HF on the 4th on the left side, and number of fluorine atoms (F) is the COF on the 3rd on the left side 2In 2 2HF with the 4th on the left side in 2 amount to 4.Thereby, help the ratio (F) of the number of hydrogen atoms (H) that reacts and number of fluorine atoms (F)/(H) become (F)/(H)=2.
Than (F)/(H) be preferably (F)/(H)〉1.5.
Then, in plasma space 26, generating CF 3OH is that the situation of intermediate gas describes as fluorine.In this case, reaction as described below takes place.
[situation 3]
(oxidizing process)
Si+2O 3→ SiO 2+ 2O 2(formula 11c)
(COF 2Generative process)
CF 3OH+H 2O → COF 2+ HF+H 2O (formula 12-1c)
(HF generative process)
COF 2+ H 2O → CO 2+ 2HF (formula 12-2c)
(HF course of dissolution)
HF+HF+4HF+2HF+4H 2O → 4HF 2 -+ 4H 3O +(formula 13c)
(etching process)
SiO 2+ 4HF 2 -+ 4H 3O +→ SiF 4+ 2H 2O+4H 2O+4HF (formula 14c)
(W-response)
Si+2O 3+ CF 3OH+HF → SiF 4+ 2O 2+ CO 2+ H 2O (formula 15c)
Shown in 12-1c, CF 3The OH instability is decomposed and is become COF 2And HF.Thereby, after this decomposes, take place the reaction identical with described situation 2 (formula 11c, 12-2c, 13c, 14c).
In formula 15c, the number of hydrogen atoms (H) that helps to react is the CF on the 3rd on the left side 31 among the HF that among the OH 1 and the left side are the 4th amounts to 2.Number of fluorine atoms (F) is the CF on the 3rd on the left side 31 in the 4th among the OH 3 and the left side amounts to 4.Thereby, help the ratio (F) of the number of hydrogen atoms (H) that reacts and number of fluorine atoms (F)/(H) become (F)/(H)=2.
Even in situation 3, also can regulate the H on silicon fiml surface by the operation substrate temperature 2O amount, thereby control reaction.
Then, show other execution modes of the present invention.
As shown in Figure 2, in the 2nd execution mode of the present invention, saved ozonizer 12.Replacing, is interflow, gas road from the fluorine of supply road 13 between humidifier 22 and plasma head 23 of oxygen supply portion 11.
In addition, also can make supply with road 13 from humidifier 22 upstream the fluorine of side be interflow, gas road.
Thus, at low dew point CF from humidifier 22 4The middle O that mixes from oxygen supply portion 11 2(mixed processes).O 2Relative CH 4Mixed proportion be preferably 5～20vol%.
This mist is directed in the plasma space 26 of plasma head 23, by plasma, from CF 4Generate COF 2In fluorine is reactant gas, simultaneously from O 2Generate O 3Deng oxidizing gas (plasma operation).Thereby, can commonization fluorine be the generating unit of reactant gas and the generating unit of oxidizing gas, can realize the simplification that constitutes.
These generate gas and are sprayed from ejection road 27, spray (jeting process) to substrate 90, utilize and the identical course of reaction of described the 1st execution mode, carry out the etching of silicon fiml 92.
The present invention is not limited to described execution mode, can carry out various changes.
For example, in the 1st execution mode, also can not mix COF from plasma head 23 2In fluorine is gas and from the ozone of ozonizer 12, supplies with to the silicon fiml surface from different ejiction openings respectively.
Can also replace ozonizer 12 with oxidizing gas, using with fluorine is that the different oxygen plasma electric discharge device of the plasma head used of gas 23 makes its generation.
After the injection of oxidizing gas, also can carry out COF 2In fluorine is the injection of reactant gas.
Embodiment 1
Embodiment 1 is described.
Use Etaching device 1 shown in Figure 1, carry out the etching of the amorphous silicon of coverlay to glass baseplate surface.As fluorine is raw material, with the CF of humidifier 22 to 0.8slm 4Middle interpolation dew point becomes the H of the amount of 13.5 ℃ (water vapor pressure 1.55kPa) 2O.This adds H 2The relative CF of O 4Flow-rate ratio be 1.55vol%.Inter-electrode space 26 importings to plasma head 23 should low dew point CF 4, plasma under atmospheric pressure.The condition of plasma is as described below.
Supply capability: 0.165kW
Service voltage: Vpp=13kV
Electrode area: 35cm 2
Utilize the gas componant after fourier-transform infrared spectroscope (FTIR) is analyzed plasma, results verification is for the CF of 1slm 4, the HF of generation 0.0057slm, the COF2 of generation 0.0149slm.
At this, at the HF of 0.0057mol and the COF of 0.0149mol 2In the ratio (F)/(H) of the number of fluorine atoms (F) that contains and number of hydrogen atoms (H) be
(F)/(H)＝(0.0149×2+0.0057)/0.0057＝6.2
Satisfy (F)/(H)〉1.5 condition.
In addition, also confirmed almost not observe plasma H afterwards 2O, for before the plasma below 1/10.
In addition, supply with the O of 0.4slm to ozonizer 12 as the raw material of oxidizing gas 2, obtain 8vol% (to O 2Than) be the O of 0.032slm 3O 3Must be at least COF 2Half the total value (0.01775slm) of volume flow (0.0057slm) of volume flow (0.0149slm) and HF more than, be preferably about its 2 times, the result we can say the O that obtains with described ozonizer 12 3Flow is for roughly preferred big or small.
Making substrate temperature is 20 ℃, mixes from the gas of described plasma head 23 with from the gas of ozonizer 12, sprays to substrate surface.
Then, measure etching speed, be 45000A/min, can obtain enough big etching speed.
Embodiment 2
In embodiment 2, detect substrate temperature and be the water addition of unstrpped gas and the relation of etching speed to fluorine.The CF of relative 0.5slm 4, regulate H with humidifier 22 2The addition of O is used 23 plasmas of plasma head then.The condition of plasma is as described below.
Supply capability: 0.165kW
Service voltage: Vpp=13kV
Electrode area: 35cm 2
In addition, use the O of 0.5slm 2, utilize ozonizer 12, make 8vol% (to O 2Ratio) O 3, it is mixed with gas after the described plasma, supply with to glass substrate, carry out the etching of the amorphous silicon film on surface
Making substrate temperature is 20 ℃, 40 ℃, 60 ℃, under each temperature conditions, measures etching speed.(wherein, 60 ℃ of common substrate temperatures for the past are comparative example).
The result as shown in Figure 3.
From with figure as can be known, substrate temperature be under 60 ℃ the situation identical with the past, is the water addition of unstrpped gas even increase to fluorine, and etching speed is variation hardly also.
Relative therewith, distinguish, be under 20 ℃ the situation at substrate temperature, become from dew point 10 ℃ the water addition near, etching speed greatly rises, become at dew point 20 ℃ the water addition near, etching speed has peak value, become at dew point 40 ℃ the water addition near, can enough be higher than the etching speed of (situations that substrate temperature is 60 ℃) in the past.
Distinguishing, is under 40 ℃ the situation at substrate temperature, in dew point is 10 ℃～40 ℃ the scope of water addition, can enough be higher than the etching speed of (situations that substrate temperature is 60 ℃) in the past.
Utilizability on the industry
The present invention can be suitable in the manufacturing such as plate glass of semiconductor wafer or liquid crystal etc. etc. Silicon fiml in etched surfaces.
1. (after the revisal) a kind of engraving method, it is the method that etching comprises the object being treated of silicon, it is characterized in that,
Generating respectively and can making the oxidizing gas of silicon oxidation and fluorine is reactant gas, and the object being treated that is set in 10 ℃～50 ℃ to temperature sprays,
Described fluorine be reactant gas to contain the non-free radical fluorine be intermediate gas, and this fluorine is that the ratio of number of fluorine atoms (F) and the number of hydrogen atoms (H) of reactant gas is (F)/(H) 1.5,
Thereby described fluorine is the reaction of intermediate gas and water generates that can to carry out etched fluorine to silica be etching gas, and to utilize this fluorine be etching gas generates water to the etching reaction of silica.
2. (after the revisal) engraving method according to claim 1 is characterized in that,
Described oxidizing gas is an ozone,
Described fluorine is that reactant gas contains as described fluorine is the COF of intermediate gas 2, containing simultaneously as described fluorine is the HF of etching gas,
The volume flow of ozone is 1/2nd and COF of the volume flow of HF 2The summation of volume flow more than.
3. (after the revisal) engraving method according to claim 2 is characterized in that,
The volume flow of described ozone is more than 2 times of described summation.
4. (after the revisal) engraving method according to claim 1 is characterized in that, described fluorine is that intermediate gas is COF 2
5. (after the revisal) engraving method according to claim 1 is characterized in that, described oxidizing gas is that oxygen is obtained by near the plasma space the atmospheric pressure.
6. (after the revisal) engraving method according to claim 1 is characterized in that,
Described fluorine is that reactant gas is that to make low dew point fluorine be that unstrpped gas obtains by near the plasma space the atmospheric pressure, and described low dew point fluorine is that unstrpped gas is to be that the water that adds dew point in the raw material and become 10 ℃～40 ℃ amount forms not having reactive fluorine with silicon.
7. (after the revisal) a kind of engraving method, it is the method that etching comprises the object being treated of silicon, it is characterized in that,
Implement:
Mix that not have reactive fluorine with silicon be that raw material, oxygen and content can make that dew point is that raw material is 10 ℃～40 ℃ a water with respect to this fluorine, thus obtain mist mixed processes and
Make this mist by near the plasma space the atmospheric pressure, thus the plasma operation of reaction of formation gas and
Be set in 10 ℃～50 ℃ object being treated to temperature and spray the jeting process of described reactant gas,
The described relatively fluorine of the ratio of the oxygen in the described mist is that raw material is 5～20vol%;
Described reactant gas contains
(a) can make silicon oxidation oxidizing gas and
(b) to contain the non-free radical fluorine be intermediate gas and number of fluorine atoms (F) and the ratio of number of hydrogen atoms (H) is (F)/(H)〉1.5 fluorine is reactant gas,
And described fluorine is thereby that the reaction of intermediate gas and water generates that can to carry out etched fluorine to silica be etching gas, and to utilize this fluorine be etching gas generates water to the etching reaction of silica.
(after the revisal) it is characterized in that according to claim 6 or 7 described engraving methods,
Described fluorine is that raw material is CF 4
(after the revisal) it is characterized in that according to claim 6 or 7 described engraving methods, the concentration by the water after the described plasma space for by before below 1/10.
(after the revisal) it is characterized in that according to claim 6 or 7 described engraving methods described dew point is 10 ℃～20 ℃.
11. (after the revisal) is characterized in that according to claim 1 or 7 described engraving methods, makes the temperature of described object being treated become 10 ℃～30 ℃.
12. (after the revisal) is characterized in that according to claim 1 or 7 described engraving methods, replaces 10 ℃, makes the lower limit of the temperature range of described object being treated become indoor dew point.
13. (after the revisal) is characterized in that according to claim 1 or 7 described engraving methods, makes the temperature of described object being treated become room temperature.

Claims (13)

1. engraving method, it is the method that etching comprises the object being treated of silicon, it is characterized in that,
Execution is set in the jeting process that 10 ℃～50 ℃ object being treated sprays reactant gas to temperature,
Described reactant gas contains:
(a) can make silicon oxidation oxidizing gas and
(b) thus contain and become with water reaction that can to carry out etched fluorine to silica be that the non-free radical fluorine of etching gas is an intermediate gas, and the ratio of number of fluorine atoms (F) and number of hydrogen atoms (H) is (F)/(H) 1.5 fluorine is reactant gas.
2. engraving method according to claim 1 is characterized in that,
Described ratio is (F)/(H)〉3.
3. engraving method according to claim 1 is characterized in that,
Described fluorine is that intermediate gas is COF 2
4. engraving method according to claim 1 is characterized in that,
Described oxidizing gas is that oxygen is obtained by near the plasma space the atmospheric pressure.
5. engraving method according to claim 1 is characterized in that,
Described fluorine is that reactant gas is that to make low dew point fluorine be that unstrpped gas obtains by near the plasma space the atmospheric pressure, and described low dew point fluorine is that unstrpped gas is to be that the water that adds dew point in the raw material and become 10 ℃～40 ℃ amount forms not having reactive fluorine with silicon.
6. engraving method according to claim 1 is characterized in that,
Described reactant gas obtains by implementing following operation, that is:
It is that raw material, relative this fluorine are water and the oxygen that the raw material dew point becomes 10 ℃～40 ℃ amount that mixing does not have with reactive fluorine of silicon, thereby obtains the mixed processes of mist; With
Make the plasma operation of described mist by near the plasma space the atmospheric pressure.
7. engraving method according to claim 6 is characterized in that,
The described relatively fluorine of the ratio of the oxygen in the described mist is that raw material is 5～20vol%.
8. according to any described engraving method in the claim 5～7, it is characterized in that,
Described fluorine is that raw material is CF 4
9. according to any described engraving method in the claim 5～7, it is characterized in that,
Concentration by the water after the described plasma space for by before below 1/10.
10. according to any described engraving method in the claim 5～7, it is characterized in that,
Described dew point is 10 ℃～20 ℃.
11. engraving method according to claim 1 is characterized in that,
Make the temperature of described object being treated be set in 10 ℃～30 ℃.
12. engraving method according to claim 1 is characterized in that,
Replace 10 ℃, make the lower limit of the temperature range of described object being treated become indoor dew point.
13. engraving method according to claim 1 is characterized in that,
Make the temperature of described object being treated become room temperature.
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