CN1149631C - A method for manufacturing a semiconductor and an apparatus for the same - Google Patents

A method for manufacturing a semiconductor and an apparatus for the same Download PDF

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CN1149631C
CN1149631C CNB941193748A CN94119374A CN1149631C CN 1149631 C CN1149631 C CN 1149631C CN B941193748 A CNB941193748 A CN B941193748A CN 94119374 A CN94119374 A CN 94119374A CN 1149631 C CN1149631 C CN 1149631C
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unit
glass substrate
solution
equipment
semiconductor film
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CN1111400A (en
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大谷久
树
安达广树
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Semiconductor Energy Laboratory Co Ltd
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Semiconductor Energy Laboratory Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers
    • H01L27/12—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body
    • H01L27/1214—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs
    • H01L27/1259—Multistep manufacturing methods
    • H01L27/127—Multistep manufacturing methods with a particular formation, treatment or patterning of the active layer specially adapted to the circuit arrangement
    • H01L27/1274—Multistep manufacturing methods with a particular formation, treatment or patterning of the active layer specially adapted to the circuit arrangement using crystallisation of amorphous semiconductor or recrystallisation of crystalline semiconductor
    • 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
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02524—Group 14 semiconducting materials
    • H01L21/02532—Silicon, silicon germanium, germanium
    • 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
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02656—Special treatments
    • H01L21/02664—Aftertreatments
    • H01L21/02667—Crystallisation or recrystallisation of non-monocrystalline semiconductor materials, e.g. regrowth
    • H01L21/02672—Crystallisation or recrystallisation of non-monocrystalline semiconductor materials, e.g. regrowth using crystallisation enhancing elements

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  • Power Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Recrystallisation Techniques (AREA)
  • Thin Film Transistor (AREA)

Abstract

In a process for crystallizing an amorphous silicon film at a low temperature using a catalyst element, a system which automatically introduces the catalyst element into the amorphous silicon film is provided. The process steps are necessary for applying a solution containing an element which accelerates the crystallization of an amorphous silicon film are each effected in units 14 to 21. The substrate is transferred by a robot arm 12.

Description

Preparation has the equipment and the method for crystalline semiconductor film
The present invention relates to have the manufacture method and the making apparatus thereof of crystalline Si semiconductor film.
Known already at present the thin film transistor (to call TFT in the following text) that uses thin film semiconductor had been arranged.This TFT is by form thin film semiconductor on substrate.Constitute with this thin film semiconductor.This TFT can utilize in various integrated circuits, but what arouse attention especially is to be utilized as the switching device of each pixel of setting liquid crystal indicator of active array type with as the driving element that forms peripheral circuit in electrooptical device.
As the thin film semiconductor that utilizes on TFT, though use amorphous silicon film simple, exist the low problem of its electrical characteristics, have crystalline silicon thin film in order to improve the characteristic of TFT, can to utilize.Have crystalline silicon fiml and can be described as polysilicon, poly-silicon, microcrystal silicon etc.In order to obtain having crystalline silicon fiml, at first to form amorphous silicon film, undertaken by heating then that crystallization finishes.
, when using heating crystallization, need be under the heating-up temperature more than 600 ℃, heating is more than 10 hours, like this under the condition if use glass is the comparison difficulty as substrate.The strain point of glass of pitted skin 7059 glass that for example is used for the liquid crystal indicator of active type is 593 ℃, when considering the large tracts of land of substrate, is heated to more than 600 ℃ and can goes wrong.
According to present inventors' research, found then to heat at elements such as the surface trace ground of amorphous silicon film deposit nickel, palladium and then aluminium, under 550 ℃, handle and just can carry out crystallization in about 4 hours.
When importing above-mentioned trace element (promoting the catalyst elements of crystallization), the method that can use plasma treatment or vapour deposition method and then ion to inject.Alleged plasma treatment is meant in the plasma CVD apparatus of parallel plate-type or anode column type, with the material that contains catalyst elements as electrode, by in the atmosphere of nitrogen or hydrogen etc., producing plasma to the method for on amorphous silicon film, adding catalyst elements.
But a large amount of catalyst elements that import, owing to can damage the reliability of semiconductor device and electric stability, so also bad.
That is, although the promotion crystallization element (catalyst elements) of above-mentioned nickel etc. is when being the amorphous silicon crystallization, and necessary element does not contain in the silicon of having wished in crystallization as much as possible.In order to reach this purpose, it is strong to be chosen in the crystallized silicon inertia tendency as catalyst elements, and the consumption with the catalyst elements of necessity is few as far as possible during crystallization simultaneously, carries out crystallization with the amount of its minimum.For this reason, must critically control the incorporation of above-mentioned catalyst elements.
In addition, during as catalyst elements, at first form amorphous silicon film, carry out the interpolation of nickel, be made into the crystallinity silicon fiml, when studying its crystallisation procedure does etc. in great detail, confirmed following item with plasma processing with nickel.
(1) when importing to nickel on the amorphous silicon film with plasma treatment, nickel has been incorporated into the suitable degree of depth part in the amorphous silicon film before heat-treating.
(2) nuclear of crystallization initial stage generation is to produce from the surface that imports nickel.
(3) with vapour deposition method nickel during film forming, can be caused crystallization with plasma processing method in the same manner on the amorphous silicon film surface.
Can draw the nickel that imports with plasma treatment from above item is not the conclusion of fully all bringing into play its effect.That is, also exist the nickel that does not play a role as yet even import a large amount of nickel.This can think to have only when nickel and silicon contact point (face), just plays a role when low temperature crystallization.But also drawn the conclusion that will as much as possible nickel be dispersed into imperceptibly the atom shape.Just following specifically conclusion, i.e. " importantly may carry out in the low temperature crystallized scope, the nickel with low concentration is dispersed into the atom shape as much as possible, imports to the near surface of amorphous silicon film ".
As the method that only imports denier nickel at the near surface of amorphous silicon film, in other words, promptly only import the method for the catalyst elements that promotes crystallization on the near surface denier ground of amorphous silicon film, can enumerate vapour deposition method, but this method exists controlled poor, and strict control catalyst element import volume is problem such as difficulty relatively.
As solution to the problems described above, the solution that has proposed to contain catalyst elements is coated on the amorphous silicon film, makes the catalyst elements of ormal weight be adsorbed on the technology of then carrying out crystallization on the amorphous silicon film surface by heat treated.
In this way, the amount by being contained in nickel in the solution, solution and amorphous silicon film time of contact, just can strict control import the concentration of the catalyst elements of amorphous silicon film.
The method of using this solution to add catalyst has a lot of advantages, but because its technology too simply also has shortcoming.So-called its shortcoming is meant the pollution of particle very sensitive.If particle can make solution not contact with coated fully when being present in coated of solution.
In addition, after catalyst elements is added operation, be necessary to heat-treat operation, but in this operation with diffusion furnace etc., also need to prevent since catalyst elements to the pollution of diffusion furnace etc.From then on viewpoint is seen, also produces the necessity that the working procedure of coating to solution manages.
The object of the present invention is to provide and use a series of series-operations, enter and use solution to import the structure of catalyst elements operation.
Fig. 1 represents the device of an example of the present invention.This device is to be coated in the surface of amorphous silicon film or to form the device that is formed the series of processes on the face of amorphous silicon film for the solution that carries out will containing continuously nickel.
As shown in Figure 1, whole device is configured in on 11 pedestals of representing with the blocking form.A plurality of substrates (in the present embodiment 20) are placed on the delivery vehicle 13, then by manipulator 12 one by one conveyance in the unit that carries out each operation.In addition, whole device will place a clean room, is less than the outside to keep inner dust amount, can reduce the pollution in the technical process like this.
Manipulator has from the structure of downside supporting substrate, and this just becomes can not pollute the surface that will carry out treatment substrate.
Below, be that example describes with the glass substrate of handling a slice.At first take out 1 glass substrate with manipulator 12 from delivery vehicle 13, conveyance determines unit 18 to the position.This determining positions unit has the function of correctly determining the substrate position on manipulator 12.This is owing to must substrate be configured in cause on the rotating platform with manipulator in the operation afterwards, at this moment, requires the center of rotating platform and the center of substrate to overlap.
After the position was determined to finish, conveyance was to cleaning unit 14.Certainly this conveyance is undertaken by manipulator 12.In cleaning unit 14, dispose rotating platform, substrate is placed on the rotating platform structure that the substrate that rotates along with rotating platform cleans with pure water.
After cleaning end, drying unit 15 is arrived in the substrate conveyance, carry out drying by manipulator 12.This drying unit 15 has can be placed on substrate the structure of carrying out heat drying on the hot plate.For this drying unit, use the air-dry dry structure of temperature just passable.
Dried substrate arrives cooling unit 16 by manipulator 12 conveyances.Cooling unit 16 is for the warmed-up substrate of cool drying operation.In this cooling unit, cool off substrate by substrate being placed on the big metal of conductive coefficient.
Cooled substrate is arrived oxidation unit by conveyance.At oxidation unit, in oxidizing atmosphere,, generate ozone by UV light from Cooper-Hewitt lamp, oxidation is carried out on the surface that forms face.This oxidation unit is in order to become air-tight state after sending into substrate, it is to be with the chamber of door to constitute by one.In oxidation unit, substrate surface forms oxide-film as thin as a wafer.
In the working procedure of coating of this oxide-film solution afterwards, can play to improve and be stained with profit characteristic purpose and as the effect that contains the support of catalyst elements compound.
As this oxidation unit the structure of carrying out thermal oxidation can be arranged, the structure that oxidizing solution that also can useful hydrogen peroxide etc. carries out oxidation.
After oxidation finishes, once more substrate is delivered to determining positions unit 18 and carried out the position and determine.Conveyance then is to coating element 19, and coating element 19 has and promotes the solution that contains catalyst elements of crystallization to be coated in on-chip function with containing.
Specifically, have the solution that to contain catalyst elements and be coated in the surface that is placed on the substrate on the rotating platform, then be rotated dry structure.Except with the spinning solution, also can pass through the method drying of air-flow or heating in solution coating back.
Then, carry out drying with drying unit 20 as required.This is because the dry inadequate cause of coating element 19.In drying unit 15 and 20, when drying means is identical, also can only use a unit in addition.
When substrate is heated in drying process, the substrate conveyance is cooled off to cooling unit 21, this operation also can be carried out in cooling unit 16.
So just on the surface of the amorphous silicon film of glass substrate, imported catalyst elements, then directly entered heating treatment step without matting.Also wish to move on to another container by manipulator from a container when entering heating treatment step, such structure is unusual effective measures for solving particle and pollution problems.
In the represented structure of Fig. 1, for each unit a determining positions mechanism can be arranged, in Fig. 1, also do not express, as appending laser annealing unit and the heat treated unit that carries out heat treated with laser radiation, and then use the unit of infrared light-struck rapid thermal annealing (RTA), also can carry out processed continuously structure in useful these unit.
Below to catalyst elements and the solution that is used to add catalyst elements describe.Can use the aqueous solution, organic solvent solution as solution.In addition, the state that is contained in the catalyst elements in the solution can be enumerated state that contains compound and the state that just disperses.
Can use as the solvent that contains catalyst elements and to elect water from polar solvent, alcohol, acid, the ammonia.
Use nickel as catalyst, when being contained in this nickel in the polar solvent, nickel adds with the nickel compound form.As the typical example of nickel compound, can use and from nickelous bromide, nickel acetate, nickel oxalate, nickelous carbonate, nickel chloride, nickel iodide, nickel nitrate, nickelous sulfate, nickel formate, nickel acetylacetonate, 4-cyclohexyl butyric acid nickel, nickel oxide, nickel hydroxide, elect.
In addition, as the solvent that contains catalyst elements, can use and elect benzene,toluene,xylene from nonpolarity solvent, carbon tetrachloride, chloroform, ether, trichloroethylene, the CFC.In addition, the polarity of saying here is not very strict, is based on that general chemical property defines.
The nickel of this moment is to import with the form of nickel compound.Can use as representational nickel compound and from nickel acetylacetonate, 2 ethyl hexanoic acid nickel, to elect.
In addition, it also is useful adding surfactant in containing the solution of catalyst elements.This is owing to can improve the adaptation to coated, the cause of control adsorptivity.This surfactant also can be coated on coated in advance.
When using monomer nickel, it must be dissolved in and make solution in the acid and use as catalyst elements.
Above-described, be to use the consoluet solution of catalyst elements nickel, needn't consoluet nickel but also can use, just for example use the powder of forming by nickel monomer or nickel compound to be evenly dispersed in emulsion material in the dispersion solvent.
Above-mentioned in addition situation is for using nickel catalyst material in addition also to be suitable for.
Use nickel as the catalyst elements that promotes crystallization, when use contains the water class polar solvent of this nickel, when directly being coated in these solution on the amorphous silicon film, often be not stained with solution, at this moment, if at first form the following thin oxide film of 100 , coating thereon then contains the solution of catalyst elements, just can apply solution equably.In addition, as by add material such as surfactant in solution, it also is effective that lubricant nature is stained with in improvement.
In addition, when using the nonpolarity solution such as toluene solution of 2 ethyl hexanoic acid nickel, can directly be coated on the amorphous silicon film surface as solution.Be effective if be coated with the materials such as driving fit agent that are applied to diaphragm coating use in advance this moment.It should be noted that and to hinder the interpolation of catalyst elements in amorphous silicon when coating amount is too much on the contrary.
The amount that is contained in the catalyst elements in the solution is also relevant with the kind of solution, general is 200ppm-1ppm to solution concentration preferably with the amount of nickel, 50ppm-1ppm (weight of nickel element is to the ratio of solution weight) preferably, this is that crystallization finishes the back by the value that nickel concentration and hydrofluoric acid resistance determined in the film.
In addition, by optionally applying the solution that contains catalyst elements, can optionally carry out crystalline growth.Particularly for the zone that does not have coating, show greatly from the zone that has applied solution with the parallel direction of the face of silicon fiml and carry out crystalline growth.The zone that this roughly grows up with the parallel direction on silicon fiml plane is called the zone of transverse crystallizing growth in this manual.
Through confirming that this its catalyst elements concentration of zone of laterally carrying out crystalline growth is low.As semiconductor device active layer zone, it is useful utilizing the crystallinity silicon fiml, but the impurity concentration in the active layer zone is generally preferably very low.Therefore, using above-mentioned zone of laterally carrying out crystalline growth, form the active layer zone of semiconductor device, is very useful for manufacturing device.
In the present invention, can obtain the most significant effect when using nickel as catalyst elements, but the kind of other utilizable catalyst elements preferably Ni, Pd, Pt, Cu, Ag, Au, In, Sn, Pd, P, As, Sb.Can also utilize one or more elements of from VIII family element, IIIb, IVb, Vb element, electing in addition.
When using Fe (iron), can use, as from ferrous bromide (FeBr as the known material of the molysite of its compound as catalyst elements 26H 2O), ferric bromide (FeBr 36H 2O), ferric acetate (Fe (C 2H 3O 2) 3XH 2O), frerrous chloride (FeCl 24H 2O), iron chloride (FeCl 36H 2O), ferric flouride (FeF 33H 2O), ferric nitrate (Fe (NO 3) 39H 2O), ferrous phosphate (Fe 3(PO 4) 28H 2O), ferric phosphate (FePO 42H 2O) elect in.
When using Co (cobalt), can use, as from cobaltous bromide (CoBr6H as the known material of the cobalt salt of its compound as catalyst elements 2O), cobalt acetate (Co (C 2H 3O 2) 24H 2O), cobalt chloride (CoCl 26H 2O), cobaltous fluoride (CoF 2XH 2O), cobalt nitrate (Co (NO 3) 26H 2O) elect in.
When using Ru (ruthenium), can use as the known material of the ruthenium salt of its compound, as ruthenic chloride (RuCl as catalyst elements 3H 2O).
When using Rh (rhodium), can use as the known material of the rhodium salt of its compound, as radium chloride (RhCl as catalyst elements 33H 2O).
When using Pd (palladium), can use as the known material of the palladium salt of its compound, as palladium bichloride (PdCl as catalyst elements 22H 2O).
When using Os (osmium), can use as the known material of the osmium salt of its compound, as osmium chloride (OsCl as catalyst elements 3).
When using Ir (iridium), can use from as the known material of the iridium salt of its compound, as from iridous chloride (IrCl as catalyst elements 33H 2O), iridic chloride (IrCl 4) in elect.
When using Pt (platinum), can use as the known material of the platinum salt of its compound, as platinum chloride (PtCl as catalyst elements 45H 2O).
When using Cu (copper), can use, as from cupric acetate (Cu (CH as the known material of the mantoquita of its compound as catalyst elements 3COO) 2), copper chloride (CuCl 22H 2O), copper nitrate (Cu (NO 3) 23H 2O) elect in.
When using gold, can use golden salt, as from gold trichloride (AuCl as its compound as catalyst elements 3XH 2O), chlorauride salt (AuHCl 44H 2O), tetrachloro gold sodium (AuNaCl 42H 2O) material of electing in.
In addition, the introduction method of catalyst not necessarily is limited in solution such as using the aqueous solution, alcohol, can use the material that contains catalyst elements widely, for example, uses the metallic compound and the oxide that contain catalyst elements.
Embodiment 1
Present embodiment is after will promoting that the catalyst elements of crystallization is contained in the aqueous solution, to be coated on the amorphous silicon film, then makes the example of its crystallization by heating.
Fig. 2 has represented the production process of present embodiment.Explanation in the present embodiment imports catalyst elements (using nickel here) process before.In the present embodiment, use corning glass 7059 as substrate 201.And its size is 100mm * 100mm.
At first, form the amorphous state silicon fiml of 100～1500 by plasma CVD method or LPCVD method.Here, the thickness of the amorphous silicon film 22 that forms with the CVD method is 1000 (Fig. 2 (A)).
201 of the substrates that below will form amorphous silicon film are called substrate.Use as the represented device of Fig. 1 the operation that nickel is imported amorphous silicon film 22 surfaces is described.
At first, the substrate 201 that has formed amorphous silicon film 22 as Fig. 2 (A) with multi-disc is configured on the delivery vehicle 13.Then with manipulator 12 the substrate conveyance is determined unit 18 to the position, after the position was determined, conveyance was carried out pure cleaning to substrate here to cleaning unit 14.
Then, the substrate conveyance to drying unit 15, is carried out 90 seconds drying under 120 ℃.Then substrate is delivered to cooling unit 16, carried out the cooling in 5 seconds.Then, again the substrate conveyance is determined unit 18 to the position, carry out the position and determine.Then, the substrate conveyance to oxidation unit 17, in oxygen atmosphere, is used UV rayed 5 minutes, form oxide-film 23 as thin as a wafer on the amorphous silicon film surface.
In addition, replace UV light, substrate can be immersed in the aquae hydrogenii dioxidi that is heated to 70 ℃ 5 minutes, also can obtain oxide-film.Can also use heat oxide film.
This oxide-film 12 can play the effect that acetate solution is coated in the whole surface of amorphous silicon in the nickeliferous acetate solution operation of coating afterwards,, is stained with lubricant nature in order that improve that is.For example, when directly acetate solution directly being coated in the amorphous silicon film surface, because amorphous silicon is not stained with acetate, so can not on the whole surface of amorphous silicon film, import nickel.That is, can not carry out the crystallization of homogeneous.
After forming oxide-film 23, to coating element 19, coating contains the acetum of nickel on substrate with the substrate conveyance.The acetate solution that promptly on the surface of amorphous silicon film 22, contains nickel by oxide-film 23 coatings as thin as a wafer.
In the present embodiment, the nickel concentration in the employed solution when being converted into weight, is 100ppm with respect to acetate solution.Working procedure of coating is undertaken by following mode.At first, with the surface of the oxide-film 23 of this acetate solution on amorphous silicon film 22 2ml that drips, this state kept 5 minutes.Then use rotating platform to be rotated drying (2000rpm, 60 seconds).(with reference to Fig. 1 (C), (D)).
What the nickel concentration in the acetum was commonly used is more than 1ppm, preferably more than 10ppm.In addition, when the nonpolarity solvent that uses as the toluene solution class of 2 ethyl hexanoic acid nickel, can not need oxide-film 23, directly catalyst elements be imported on the amorphous silicon film.
By 1 time to the working procedure of coating that carries out this nickel solution for several times, can on the surface of the amorphous silicon film behind the Rotary drying 22, form the nickel dam that contains with several ～hundreds of average film thickness.At this moment, in the nickel of this layer heating process afterwards, can be spread in the amorphous silicon film, play the catalyst action that promotes crystallization.Moreover this layer is not limited to become complete film.
After being coated with above-mentioned solution, under this state, kept 5 minutes.Length according to the retention time can be controlled the concentration that is contained in the final nickel in the silicon fiml 22, but maximum governing factor still is the concentration of solution.
After coating ends, substrate 20 is carried out drying from working procedure of coating 19 conveyances to drying unit, and then in cooling unit 21, cool off.
So, use the operation of Fig. 1 device to finish.Then, in heating furnace, in blanket of nitrogen, under 550 ℃, carry out 4 hours heat treated.Its result can obtain on substrate 201 forming and has crystalline silicon thin film 22.
Above-mentioned heat treated can be carried out in the temperature more than 450 ℃, but temperature just must prolong heating time when low, and production efficiency also just descends.In addition, if when carrying out more than 550 ℃, the thermal endurance problem of glass substrate as substrate will appear using.
Be that explanation imports the method for catalyst elements in the present embodiment on amorphous silicon film, but also can adopt the method that under amorphous silicon film, imports catalyst elements.At this moment, be before the film forming of amorphous silicon film, use the solution contain catalyst elements, on underlying membrane, import catalyst elements.
Embodiment 2
In the present embodiment, use the crystalline silicon fiml that has of embodiment 1 making, the example of the TFT on each pixel parts of liquid crystal indicator that is arranged on active array type is made in expression.In addition,, be not only liquid crystal indicator, can certainly utilize in general thin film integrated circuit as the range of application of TFT.
At first, the crystallinity silicon fiml that will produce according to embodiment 1 represented operation forms the zone 104 of island with scribing.This island areas 104 has constituted the active layer of TFT.And formed thickness 200～1500 , be the silica 105 of 1000 here.This silicon oxide film also plays gate insulating film (Fig. 3 (A)).
Must note meticulously when making above-mentioned silicon oxide film 105.Here being to be raw material with TEOS, with oxygen, is 150～600 ℃ at substrate temperature, preferably under 300～450 ℃, decomposes the silicon oxide deposition film with the RF plasma CVD method.The pressure ratio of TEOS and oxygen is 1: 1～1: 3, and in addition, pressure is 0.05～0.5torr, and RF power is 100～250W.Perhaps be raw material with TEOS with ozone by decompression CVD method or atmospheric pressure cvd method, 350～600 ℃ of substrate temperatures, preferably 400～550 ℃ form down.After the film forming, in the atmosphere of oxygen or ozone, under 400～600 ℃, annealed 30～60 minutes.
Under this state,, also can promote the crystallization of silicon area 104 with KrF excimer laser (wavelength 248nm, arteries and veins swell wide 20nsec) or the strong illumination equal with it.Particularly use not heating glass substrate and only selectively heat silicon of infrared light RTA (rapid thermal annealing), and owing to can reduce interface energy level on silicon and the silicon oxide film interface, so be favourable for making the insulated-gate type field effect semiconductor device.
Then, form the aluminium film of thick 2000 ～1 μ m, it is carved into figure, form gate electrode 106 with the electron beam vapour deposition method.In aluminium, can also mix the scandium (Sc) of 0.15～0.2% (weight).Then substrate being immersed in 1～3% the tartaric acid ethylene glycol solution of pH=7, is negative electrode with platinum, is anode with this aluminum gate electrode, carries out anodic oxidation.Anodic oxidation is to make voltage be raised to 220V with certain electric current at first, finishes after keeping 1 hour under this state.In the present embodiment, be under the constant current state, the rising speed of voltage is suitable 2～5V/ branch.Through handling like this, can form thickness 1500～3500 , for example the anodic oxide 109 of 2000 .(Fig. 3 (B)).
Then, with ion doping method (also claiming the plasma doping method) in the island silicon fiml of each TFT, with gate electrode as mask autoregistration ground implanted dopant (phosphorus).Use hydrogen phosphide (PH as impurity gas 3).Dosage is 1～4 * 10 15Cm -2
And then, shown in Fig. 3 (C),,, can improve the crystallinity of crystallinity deterioration part to above-mentioned zone of mixing impurity with KrF excimer laser (wavelength 248nm, the wide 20nsec of pulse) irradiation.The energy density of laser is 150～400mJ/cm 2, 200～250mJ/cm preferably 2Form N type impurity (phosphorus) zone 108,109 like this.These regional sheet resistances are 200～800 Ω/.
In this operation, replace laser, also can use photoflash lamp, make it to rise in the short time 1000～1200 ℃ (silicon monitor temperature), sample is heated promptly so-called RTA (rapid thermal annealing) (also claiming RTP, rapid hot technics).
Then, be by being raw material with TEOS as comprehensive insulant 110, by the plasma CVD method of itself and oxygen, perhaps forming thickness with the decompression CVD method of ozone or atmospheric pressure cvd method is the silicon oxide film of 3000 .Substrate temperature is 250～450 ℃, for example 350 ℃.Have an even surface this silicon oxide film of available mechanical lapping after the film forming in order to make.And then with sputtering method deposit ITO film, it is carved into figure after, as pixel capacitors 111.(Fig. 3 (D))
Then, insulant 110 between etch layer, as shown in Fig. 1 (E), in the source of TFT/drain region forms contact hole, forms the wiring 112,113 of chromium or titanium nitride, wiring 113 are connected with pixel capacitors 111.
After using plasma treatment, and the crystallinity silicon fiml of importing nickel compares with silicon oxide film, and is lower for the selectivity ratios of buffered hydrofluoric acid, so often be etched away in above-mentioned contact hole formation operation.
, in the present embodiment, when the aqueous solution of the low concentration of use 10ppm imports nickel, because the hydrofluoric acid resistance height so the above-mentioned contact hole that forms is stable, can reproduce out well.
At last, in hydrogen,, finished the hydrogenation of silicon with 300～400 ℃ of annealing 0.1～2 hour.So also just finished the making of TFT.And a plurality of TFT that will make simultaneously be arranged in rectangular after, then finished active array type LCD.This TFT has source/drain region 108/109 and passage forms district 114.In addition, the 115 electrical engagement parts that become NI.
When adopting the structure of present embodiment, the concentration that is present in nickel in the active layer is 3 * 10 18Cm -3About or following, 1 * 10 16Atoms cm -3～3 * 10 18Atoms cm -3
Adopt structure of the present invention, can obtain the crystallinity silicon fiml at low temperatures expeditiously.
Moreover the layer that contains catalyst in an embodiment forms on amorphous silicon film, is pre-formed the layer that contains catalyst on substrate, and forming amorphous silicon film thereon also is within the scope of the invention.
The simple declaration of accompanying drawing
Fig. 1 represents the structure of embodiment.
Fig. 2 represents the production process of embodiment.
Fig. 3 represents the production process of embodiment.
The explanation of symbol
11 ... pedestal
12 ... manipulator
13 ... delivery vehicle
14 ... cleaning unit
15 ... drying unit
16 ... cooling unit
17 ... oxidation unit
18 ... the determining positions unit
19 ... coating element
20 ... drying unit
21 ... cooling unit
201 ... glass substrate
22 ... silicon fiml
23 ... oxide-film
25 ... rotating platform

Claims (19)

1. preparation has the method for crystalline semiconductor film, and described method comprises:
On glass substrate, form the described semiconductor film that comprises amorphous silicon;
Preparation comprises following equipment,
Be positioned at the carrier unit on the pedestal, described carrier unit is used for placing glass substrate thereon,
Be positioned at least one oxidation unit on the pedestal, described oxidation unit is used for the surface of oxidation glass substrate,
Be positioned at the determining positions unit on the pedestal, described determining positions unit is used for determining the position of glass substrate,
Be positioned at least one cleaning unit on the pedestal, described cleaning unit is used to clean glass substrate,
Be positioned at least one coating element on the pedestal, described coating element is used for the surface of solution coat at glass baseplate,
Be positioned at least one drying unit on the glass substrate, described drying unit is used for the dry glass substrate,
Be positioned at least one cooling unit on the pedestal, described cooling unit be used for the cooled glass substrate and
Be positioned at the carrying device on the pedestal, described carrying device is used for substrate by a unit conveyance of said units to another unit;
By described carrying device described oxidation unit is arrived in described glass substrate conveyance;
Form thin oxide layer at the described glass substrate of described oxidation unit oxidation on the surface at semiconductive thin film, described thin oxide layer can be assigned to described catalyst material the whole surface of semiconductor film;
By described carrying device coating element is arrived in described glass substrate conveyance; With
Form the solution that contains catalyst material that contacts with the surface of described semiconductive thin film, so that continuous layer to be provided on the surface of described semiconductor film, described catalyst material can promote the crystallization of described amorphous silicon.
2. the process of claim 1 wherein that described solution comprises nickel solution.
3. the process of claim 1 wherein that described catalyst material is be selected from Ni, Pd, Pt, Cu, Ag, Au, In, Sn, P, As and Sb at least a.
4. the process of claim 1 wherein that the step that forms the solution contain catalyst material carries out at least once.
5. the process of claim 1 wherein that entire equipment places clean room.
6. the process of claim 1 wherein that thickness of oxide layer is no more than 100 .
7. the process of claim 1 wherein that described solution is be selected from polar solvent, non-polar solven and surfactant at least a.
8. preparation has the equipment of crystalline semiconductor film, and described equipment comprises:
Be used for determining at least one determining positions unit of glass substrate position,
Be used to clean the cleaning unit of described glass substrate,
With the lip-deep coating element that the solution paint is provided at the described semiconductor film that comprises amorphous silicon on the described glass substrate, described solution contains the catalyst elements that promotes described semiconductor film crystallization,
Be used for glass substrate by a conveyance of said units to another carrying device and
Place the carrier unit of a plurality of glass substrates thereon,
Wherein, described cleaning unit, coating element, carrying device and carrier unit are positioned at same equipment.
9. the equipment of claim 8, the wherein said equipment that is used to prepare semiconductor device has the drying unit that at least one is used for dry described solution.
10. the equipment of claim 8, wherein said equipment has at least one oxidation unit that is used for the surface of oxide-semiconductor film.
11. the equipment of claim 8, wherein said equipment have at least one cooling unit that is used for the cooled glass substrate.
12. the equipment of claim 8, wherein said catalyst elements are be selected from Ni, Pd, Pt, Cu, Ag, Au, In, Sn, P, As and Sb at least a.
13. the equipment of claim 8, wherein entire equipment places clean room.
14. the equipment of claim 8, wherein said solution are be selected from polar solvent, non-polar solven and surfactant at least a.
15. the equipment of claim 8, it also comprises and is used for by heating the crystalline element of the described semiconductor film of described solution crystallization that contacts with the described surface of described semiconductor film.
16. preparation has the method for crystalline semiconductor film, this method comprises:
Provide a plurality of glass substrates in carrier unit, wherein each glass substrate provides the described semiconductor film that comprises amorphous silicon;
By carrying device with one of glass substrate by the carrier unit conveyance to cleaning unit;
Clean the surface of one of described glass substrate at cleaning unit;
By described carrying device with one of glass substrate by the cleaning unit conveyance to coating element;
Apply the solution paint is provided on the surface of the semiconductor film on one of described glass substrate, described solution contains the catalyst elements that promotes described semiconductor film crystallization; With
One of dry glass substrate,
Wherein, carrier unit, cleaning unit, coating element and carrying device are arranged in same equipment at least.
17. according to the method for claim 16, wherein said catalyst elements is be selected from Ni, Pd, Pt, Cu, Ag, Au, In, Sn, P, As and Sb at least a.
18., wherein be used for preparing the whole clean room that places of equipment of semiconductor device according to the method for claim 16.
19. according to the method for claim 16, wherein said solution is be selected from polar solvent, non-polar solven and surfactant at least a.
CNB941193748A 1993-12-03 1994-12-03 A method for manufacturing a semiconductor and an apparatus for the same Expired - Fee Related CN1149631C (en)

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JP339586/1993 1993-12-03
JP33958693 1993-12-03
JP339586/93 1993-12-03

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JP3674864B2 (en) * 2003-03-25 2005-07-27 忠素 玉井 Vacuum processing equipment
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