CN1849700A - Multilayer substrate cleaning method, substrate bonding method, and bonded wafer manufacturing method - Google Patents
Multilayer substrate cleaning method, substrate bonding method, and bonded wafer manufacturing method Download PDFInfo
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- CN1849700A CN1849700A CN 200480026098 CN200480026098A CN1849700A CN 1849700 A CN1849700 A CN 1849700A CN 200480026098 CN200480026098 CN 200480026098 CN 200480026098 A CN200480026098 A CN 200480026098A CN 1849700 A CN1849700 A CN 1849700A
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Abstract
The present invention is a method for cleaning a multilayer substrate with a cleaning liquid capable of etching a protective film formed on the surface of an SiGe layer which is the outermost layer of the multilayer substrate in such a way that the protective film is left. A method for bonding a multilayer substrate cleaned by the above method in sucha way that the outermost layer of the multilayer substrate is bonded to the surface of another substrate. A bonded wafer manufacturing method in which an Si1-xGex layer and a protective layer are sequentially formed on an Si single-crystal bonded wafer, ions are implanted through the protective film to form an ion-implanted layer, the bonded wafer is cleaned, the surface of the protective layer is brought into close contact with a base wafer, separation is carried out at the ion-implanted layer, a thermal oxide layer is formed on the surface of a separation layer transferred to the base wafer by the separation, the thermal oxide layer is removed to expose a concentration SiGe layer, and an Si single-crystal layer is epitaxially grown on the surface of the concentration SiGe layer. With these, a cleaning method not roughening the surface of the SiGe layer which is the outermost layer of a multilayer substrate, a bonding method, and a bonded wafer manufacturing method by which defective bonding attributed to ion implantation can be prevented are provided.
Description
Technical field
The present invention relates to have washing methods and the applying method of substrate and the manufacture method that is manufactured on the bonded wafer that has silicon epitaxy layer on the germanium-silicon layer of the multilager base plate of germanium-silicon layer.
Background technology
In recent years, in order to cooperate the demand of high-speed semiconductor element, openly MOSFET (the Metal-Oxide Semiconductor field-effect transistor of high speed of motion is arranged; Metal-Oxide-SemiconductorField Effect Transistor) semiconductor element such as, described semiconductor element with SiGe (SiGe) layer between middle and silicon layer that growing epitaxial forms on silicon substrate uses in the raceway groove field.
In this case, for the silicon crystallization, the SiGe crystallization is because lattice constant is bigger, and the silicon layer of being grown on germanium-silicon layer can produce stretcher strain (is strained silicon layer to call the silicon layer that produces this distortion in the following text).By this distortional stress, (energy band) structure of being with of silicon crystallization can change, the result, and the degenerate solution that can be with removes, and forms high being with of carrier mobility.Therefore, use this strained silicon (strainedsilicon) layer to be general transistorized about 1.3～8 times as the high speed motion characteristic that MOSFET showed of raceway groove.
Owing to the size of the stretcher strain that is produced in strained silicon layer becomes big along with the germanium concentration of germanium-silicon layer increases, so the germanium concentration of germanium-silicon layer is an important parameters.Below be that the germanium-silicon layer of X (0＜X＜1) is recited as Si with the germanium ratio of components
1-XGe
XLayer.
Form the method for this strained silicon layer, except as above-mentioned prolong beyond the method for method as main body, for example known spy of having opens 2001-217430 communique and spy and opens the 2002-164520 communique and openly make and have SOI (Silicon-On-Insulator; Silicon On Insulator) the applying SOI substrate of structure is to form Si in conjunction with silicon substrates such as wafers
1-XGe
XLayer makes oxide-film between the centre, with the Si of formation in conjunction with wafer
1-XGe
XLaminar surface and silicon substrate are fitted, and subsequently, the silicon substrate in conjunction with wafer are carried out the method etc. that filming is used as strained silicon layer.At this moment, open the 2002-164520 communique as the spy, openly also can be as required to Si
1-XGe
XLayer carries out the surface heat oxidation, is used as improving the si-enriched germanium layer of concentration.
At this moment, in conjunction with the filming of the silicon substrate of wafer, can be by grinding polishing, PAGE (plasma-assisted chemical etching method; Plasma Assisted Chemical Etching) vapor phase etchant such as method or ion inject and peel off method (being also referred to as SMARTCUT (registered trade mark) method) and wait and carry out.
Ion injects peels off method from the surface in conjunction with wafer, just at Si
1-XGe
XLaminar surface inject at least hydrogen ion or noble gas ion wherein a kind of, in conjunction with wafer inside, for example near surface forms the micro-bubble layer, make oxide-film between the centre, after will sticking together in conjunction with the ion injection face side of wafer and matrix wafer, apply heat treatment (peeling off heat treatment) and small gas made as parting plane (release surface) be film like and peel off in conjunction with wafer, so apply heat treatment (in conjunction with heat treatment) make two wafer massively in conjunction with and as the technology of bonded wafer.
The spy opens the 2002-305293 communique and is disclosed in and is formed with Si on the silicon substrate
1-XGe
XIn the silicon substrate in conjunction with wafer of layer, silicon layer, insulating barrier, inject by ion and to form separating layer, make this surface applying matrix wafer in conjunction with the insulating barrier of wafer.And open, peel off in separating layer subsequently, will move the silicon layer of the peel ply of being located at the matrix wafer side as strained silicon layer.
Usually, the adhesive substrates of bonded wafer etc. unfavorable condition such as peels off in order to prevent to produce at binding face, wishes that binding face has high adhesion.Usually, the evaluation of the adhesion of adhesive substrates binding face can be undertaken by the surface energy (proportional with adhesion) of estimating binding face.The mensuration of surface energy can be used the spy to open the disclosed razor insertion of flat 7-29782 communique and carry out.
The spy opens the 2001-217430 communique openly makes oxide-film between the centre, when other silicon substrate is fitted on the surface of germanium-silicon layer, must wash binding face before applying, removes the particulate or the pollutant on surface.At this washing process, use wherein a kind of NH of general cleaning solution of silicon substrate usually
4OH and H
2O
2Mixed aqueous solution (SC-1:, just carry out SC-1 washing standard wash liquid 1) as cleaning solution.
Summary of the invention
As mentioned above, use ion to inject the situation of peeling off the manufactured bonded wafer, when carrying out the ion injection, at the Si of injection face
1-XGe
XSurfaces such as layer, silicon layer, insulating barrier can produce organic substance or metal impurities etc. and pollute or take place the rough surface situation, and after ion injects, because of oxide-film makes Si between the centre
1-XGe
XWhen surfaces such as layer and base wafer were sticked together, the binding face after peeling off heat treatment can produce space (void) or pore (blister) etc. in conjunction with bad problem.This space or pore can make the manufacturing output of bonded wafer reduce.
At this moment, SC-1 washing as the aforementioned be can consider to carry out, surperficial organic substance or metal impurities etc. removed.
When silicon substrate is applied the SC-1 washing, because the surface of silicon substrate can be by etching removal a little, so clean result is good.But apply SC-1 washing with respect to the surface to silicon layer, when the surface of germanium-silicon layer was applied the SC-1 washing, the germanium-silicon layer surface roughness after can cleaning became coarse significantly.According to this case inventor's etc. investigation, this is that the etch-rate of germanium is very fast, can clear this surface roughness become big along with the rising of germanium concentration owing to compare with the etching speed of silicon.Therefore, when baseplate-laminatings such as the surface of the washed like this germanium-silicon layer of use and silicon substrate were made adhesive substrates, the adhesion of binding face can reduce.It is to carry out subsequently such as in conjunction with steps such as wafer filmings the time that the adhesion of this binding face reduces, the reason that causes binding face to peel off, thereby cause the manufacturing efficient of adhesive substrates to reduce.
For example, when making aforementioned bonded wafer, make oxide-film between fit Si after cleaning of the mode of centre
1-XGe
XUnder the surface of layer and the situation of base wafer, the binding face after peeling off heat treatment can produce space or pore etc. in conjunction with bad problem.
And, make Si
1-XGe
XWhen silicon layer on the layer and insulating barrier are fitted between the centre and with base wafer, work as Si
1-XGe
XWhen the Ge concentration of layer is high,, the possibility that produces transposition is arranged because the lattice relaxation in the si-enriched germanium layer (latticerelaxation) can't carry out fully.In this case, also variation of the crystallinity of the strained silicon layer directly over germanium-silicon layer.
In view of above problem realizes the present invention, first purpose of the present invention provides a kind of washing methods and applying method, it can prevent to produce the shaggy problem of germanium-silicon layer when washing has germanium-silicon layer at least as the multilager base plate on top layer, and prevents to take place when follow-up manufacturing adhesive substrates the problem that the adhesion of binding face reduces.
Second purpose of the present invention provides a kind of manufacture method of bonded wafer, and it can prevent to use the ion injection to peel off Fa Shiyin and be attached to Si along with the ion injection
1-XGe
XThe organic substance of layer or pollution such as metal impurities or space that rough surface produced or pore etc. are in conjunction with the generation of bad problem, and can prevent at Si
1-XGe
XLayer produces transposition, and can the good strained silicon layer of growth quality.
In order to reach above-mentioned first purpose; the invention provides a kind of washing methods of multilager base plate; it has the washing methods of germanium-silicon layer as the multilager base plate on top layer at least; this method forms diaphragm on the surface of aforementioned germanium-silicon layer at least; subsequently, the 1st cleaning solution by can the aforementioned diaphragm of etching has the mode of aforementioned diaphragm to wash aforementioned multilager base plate with remnants.
Like this, after the germanium-silicon layer surface formed diaphragm, when having the mode of aforementioned diaphragm to wash aforementioned multilager base plate by the 1st cleaning solution with remnants, this diaphragm can protect germanium-silicon layer to prevent rough surface when washing.And, because by the 1st cleaning solution a little etching remove diaphragm, reduce with the adhesion that prevents binding face and can improve clean result.
At this moment, be preferably composition, temperature or washing time, adjust the thickness of aforementioned remaining diaphragm by adjusting the 1st cleaning solution.
By composition, temperature or the washing time of adjusting the 1st cleaning solution, can easily adjust the residual thickness of diaphragm, make diaphragm have suitable thickness.
And the preferably is that the following mode of above 100 nanometers is washed so that the thickness of aforementioned remaining diaphragm is 1 nanometer.
The thickness that makes remaining diaphragm is when 100 nanometers are following more than 1 nanometer; can protect by abundant thickness can be because of washing the rough surface that is produced; and subsequently; when making bonded wafer, also can obtain from strained silicon layer to thickness between oxide-film enough thin bonded wafer with strained silicon layer by fitting.
At this moment, aforementioned diaphragm can be made of silicon, and the 1st cleaning solution can be by NH
4OH and H
2O
2Mixed aqueous solution constitute.
When aforementioned diaphragm is to be made of silicon, and the 1st cleaning solution is by NH
4OH and H
2O
2Mixed aqueous solution and during as so-called SC-1 cleaning solution, it can fully improve clean result in the shaggy while of the diaphragm that prevents binding face, and prevents that fully the adhesion of binding face from reducing.
And; also can be by can the aforementioned diaphragm of etching and the etch-rate of aforementioned diaphragm removed aforementioned diaphragm less than the 2nd cleaning solution of the 1st cleaning solution, so that the mode that aforementioned germanium-silicon layer exposes is washed through the washed multilager base plate of aforementioned the 1st cleaning solution.
When by can the aforementioned diaphragm of etching and remove aforementioned diaphragm less than the 2nd cleaning solution of the 1st cleaning solution than the etch-rate of aforementioned diaphragm; so that the mode that aforementioned germanium-silicon layer exposes is washed when the washed multilager base plate of aforementioned the 1st cleaning solution; because germanium-silicon layer is by the 2nd less cleaning solution of etch-rate; can not can to produce shaggy mode etched; can be in the shaggy while of the germanium-silicon layer that prevents binding face; can improve clean result fully, and prevent that the adhesion of binding face from reducing.
And the 2nd cleaning solution can be by NH
4OH and H
2O
2Mixed aqueous solution constitute.
Like this, use the NH slower than the etch-rate of the 1st cleaning solution
4OH and H
2O
2The 2nd cleaning solution of mixed aqueous solution when being used as the SC-1 cleaning solution, it can prevent the shaggy while of germanium-silicon layer of binding face, can improve clean result fully, and prevents that fully the adhesion of binding face from reducing.
At this moment, be preferably the temperature that the temperature that makes the 2nd cleaning solution is lower than the 1st cleaning solution.
Like this, when the temperature that makes the 2nd cleaning solution is lower than the temperature of the 1st cleaning solution, the etch-rate of the 2nd cleaning solution can not make germanium-silicon layer generation rough surface phenomenon because can easily be reduced, it prevented as the shaggy while of the germanium-silicon layer of binding face, can have very high clean result, can prevent fully that the adhesion of binding face from reducing.
And; the invention provides a kind of applying method of substrate; its make through above-mentioned multilager base plate washing methods the germanium-silicon layer on the top layer of washed multilager base plate or the surface of diaphragm, with directly or make dielectric film come to fit with the surface of other its plate between the mode of centre.
The most surperficial and when preventing that the germanium-silicon layer that the shaggy while was washed fully or the surface of the surface of diaphragm and other its plate from fitting when making outside the washed multilager base plate of above-mentioned multilager base plate washing methods; can prevent problem because of the reduction of binding face adhesion that rough surface produces; therefore in technology subsequently; binding face can not produce because of rough surface causes adhesion and reduce, and helps to promote the manufacturing output of adhesive substrates.
And, in order to reach above-mentioned second purpose, the invention provides a kind of manufacture method of bonded wafer, comprise following steps: form Si on surface at least in conjunction with the silicon single crystal wafer of wafer
1-XGe
XLayer (0＜X＜1); At this Si
1-XGe
XThe surface of layer forms protective layer; One of them forms ion implanted layer at least to inject at least hydrogen ion or noble gas ion by this protective layer; The washing be formed with this ion implanted layer in conjunction with wafer; With after this washing in conjunction with the wafer protection laminar surface so that oxide-film between middle or directly mode and matrix wafer stick together; Peel off from aforementioned ion implanted layer subsequently; Form heat oxide film to carrying out thermal oxidation because of aforementioned surface of peeling off the peel ply that moves to the matrix wafer side; Expose the si-enriched germanium layer that germanium is concentrated by the heat oxide film of removing this formation; Make the surperficial epitaxial growth of this si-enriched germanium layer that exposes go out monocrystalline silicon layer.
Like this, form Si successively on surface in conjunction with the silicon single crystal wafer of wafer
1-XGe
XBehind layer (0＜X＜1) and the protective layer; one of them person who injects hydrogen ion or noble gas ion by this protective layer forms ion implanted layer; washing subsequently be formed with this ion implanted layer in conjunction with wafer the time produce Si because can prevent because of washing by protective layer
1-XGe
XThe problem that laminar surface is coarse can be removed and be attached to organic substance or the metal impurities that inject the surface simultaneously when injecting ion, produces space or pore to prevent the binding face after peeling off heat treatment.And; make after this washing in conjunction with the wafer protection laminar surface with dielectric films such as silicon oxide layers between middle or when directly mode and matrix wafer stick together; the interface of protective layer and matrix wafer becomes and slides easily; when subsequently the surface of peel ply being carried out thermal oxidation and forms heat oxide film, can suppress Si
1-XGe
XThe germanium of layer is concentrated and the si-enriched germanium layer that forms produces transposition, can carry out lattice relaxation fully simultaneously.Therefore, can be at the second best in quality strained silicon layer of this surface epitaxial growth.
And, when washing like this, can use aforesaid multilager base plate washing methods.At this moment, on the surface of monocrystalline silicon, form Si at least in conjunction with wafer
1-XGe
XLayer is at this Si
1-XGe
XForm protective layer on the table of layer; injecting hydrogen ion by this protective layer waits and forms ion implanted layer; by cleaning solution that can the aforementioned protective layer of etching, carry out the so-called washing process that the mode of aforementioned protective layer is arranged with remnants in conjunction with wafer to what this was formed with ion implanted layer.
At this moment, make aforementioned X less than 0.2 for good, with below 0.15 for better.
When the concentration of germanium is following less than 20%, particularly 15%, this Si
1-XGe
XThe transposition of layer is rare.
And forming in monocrystalline silicon layer, amorphous silicon layer, polysilicon layer or the silicon oxidation rete one of them kind, to be used as this protective layer be preferable.
When aforementioned protective layer was described silicon layer, it had sufficient protective layer function, and can easily form by methods such as vapor phase growths.And, if when protective layer is the silicon oxidation rete, also can form, and after applying, also can be used as the BOX layer and (imbed oxide-film by thermal oxidation; Buried Oxide).
And, also can carry out aforementioned ion and inject in the direction vertical with aforementioned protective layer.
The channeling effect that produces (or claiming tunneling effect) when preventing that ion from injecting is carried out ion with incline direction and is injected to goodly, but can make the inner evenness variation of injection thickness distribution.And the inventive method forms diaphragm, and to carry out ion when injecting with protective layer Surface Vertical direction, can improve the inner evenness that ion injects the degree of depth, and form good ion implanted layer.When particularly protective layer is retes such as silicon oxidation rete, amorphous silicon layer, polysilicon layer, can prevent to produce channeling effect effectively.
At this moment, employed dielectric film when the protective layer surface in conjunction with wafer after the aforementioned washing is sticked together with the aforementioned substrates wafer is preferably the surface that only is formed at the aforementioned substrates wafer.
Like this; when protective layer is binding face with the interface that only is formed on the dielectric film of matrix wafer surface; because be easy to generate slip at this binding face; in the technology of back, pass through to form heat oxide film; the si-enriched germanium layer that this germanium concentration is enhanced can easily carry out lattice relaxation, and can suppress to produce transposition in the si-enriched germanium layer.At this moment, to use silicon single crystal wafer or the insulating properties wafer is preferable as the aforementioned substrates wafer.
When the matrix wafer is silicon single crystal wafer, can easily form dielectric film by thermal oxidation or vapor growth method etc., this dielectric film is produced between the centre and with the protective layer surface that combines wafer stick together.And, also can the join protection layer directly be fitted with insulating properties matrix wafers such as quartz, carborundum, aluminium oxide, diamonds according to purposes.
Temperature when at this moment, the germanium of si-enriched germanium layer is come on the aforementioned peel ply of thermal oxidation surface is for preferable more than 900 ℃.
When the oxidate temperature on peel ply surface is more than 900 ℃ the time, can prevent that the interface of oxide-film and germanium-silicon layer from the phenomenon that germanium is separated out taking place.
And, thermal oxidation is carried out on aforementioned peel ply surface so that the temperature of the silicon layer on surface when becoming heat oxide film with below 1000 ℃ for preferable.
When thermal oxidation is carried out on the surface of aforementioned peel ply so that the temperature of the silicon layer on surface when becoming heat oxide film is below 1000 ℃ the time, inject the damage that produces by ion in the silicon layer remnants on peel ply surface, when being accommodated, can prevent to produce OSF (oxygen induction multilayer defective by formed heat oxide film; Oxidation induced Stacking Fault) defective such as.
According to the present invention, when using the 1st cleaning solution to have the mode of diaphragm to wash this diaphragm with remnants after the germanium-silicon layer surface forms diaphragm, it can be protected germanium-silicon layer and prevent this germanium-silicon layer rough surface when washing.And, because come etching a little to remove this diaphragm, can improve and wash the bar effect, and prevent that the adhesion of binding face from descending by the 1st detergent remover.
And; can the aforementioned diaphragm of etching and the etch-rate of aforementioned diaphragm 2nd cleaning solution littler than the 1st cleaning solution removed aforementioned diaphragm to using through the washed multilager base plate of aforementioned the 1st cleaning solution; so that the mode that aforementioned germanium-silicon layer exposes is when washing; because by the 2nd less cleaning solution of etch-rate; can can not produce shaggy mode with germanium-silicon layer and carry out etching; and in the shaggy while of germanium-silicon layer that prevents to become binding face; can improve clean result fully, and prevent that fully the adhesion of binding face from reducing.
And; use the washed germanium-silicon layer of above-mentioned washing methods or the surface of the surface of protective layer and other substrate with directly or make dielectric film when the mode of centre is fitted; can prevent because of the caused adhesion decline of the rough surface of binding face problem; and binding face can not produce such as bad problem such as peeling off in technology subsequently, helps to promote the manufacturing output of adhesive substrates.
And, according to the present invention, on surface, form Si successively in conjunction with the silicon single crystal wafer of wafer
1-XGe
XBehind layer (0＜X＜1), the protective layer; by this protective layer inject hydrogen ion or noble gas ion at least one of them to form ion implanted layer; subsequently, the washing be formed with this ion implanted layer in conjunction with wafer the time because by protective layer can prevent because of the washing Si that produces
1-XGe
XThe problem that laminar surface is coarse can be removed when ion injects and be attached to organic substance or the metal impurities that inject the surface simultaneously, can prevent that the binding face after peeling off heat treatment from producing space or pore.Make after the washing in conjunction with wafer protection laminar surface and matrix wafer with dielectric films such as silicon oxide layers between middle or when it is sticked together; the interface of protective layer and matrix wafer becomes and is easy to generate slip; when subsequently the surface of peel ply being carried out thermal oxidation and forms heat oxide film, can suppress Si
1-XGe
XThe germanium of layer is concentrated and the si-enriched germanium layer generation transposition that forms, can carries out lattice relaxation fully simultaneously.Therefore, can be at the second best in quality strained silicon layer of this surface epitaxial growth.
Description of drawings
Fig. 1 is the schematic diagram of the example of multilager base plate washing process of the present invention.
Fig. 2 is the schematic diagram of another example of multilager base plate washing process of the present invention.
Fig. 3 is the schematic diagram of the attaching process of multilager base plate of the present invention.
Fig. 4 is the schematic diagram of the example of bonded wafer technology of the present invention.
Fig. 5 is the schematic diagram of another example of bonded wafer technology of the present invention.
Fig. 6 is the figure of the surface energy value when the sample wafer of embodiment 1,2 and comparative example 1～3 and matrix wafer are fitted.
Fig. 7 is when changing the liquid temperature of SC-1 cleaning solution, the etching spirogram on the top layer of the sample wafer of embodiment 3 and comparative example 4.
Wherein, description of reference numerals is as follows:
1 multilager base plate, 2 germanium-silicon layers
3 diaphragms, 4 top layers
5 matrix wafers 11, silicon single crystal wafer
11 ' silicon single crystal wafer
12, germanium-silicon layer 13, protective layer
12 ' germanium-silicon layer, 13 ' protective layer
14, ion implanted layer 15, matrix wafer
14 ' ion implanted layer, 15 ' matrix wafer
16, silicon oxide layer 17 silicon layers
16 ' silicon oxide layer
18, heat oxide film 19, si-enriched germanium layer
18 ' heat oxide film, 19 ' si-enriched germanium layer
20 monocrystalline silicon layers, 17 ' germanium-silicon layer
Embodiment
Embodiments of the invention below are described, but the present invention is not limited thereto.
As previously mentioned; when forming strained silicon layer; use is formed germanium-silicon layer surface on the silicon substrate that becomes in conjunction with wafer; make oxide-film when the method for other substrate is fitted in the centre; surface particle or pollutant in order to remove binding face before applying; employed SC-1 washing etc. when germanium-silicon layer is applied common washing silicon substrate; because the etch-rate of germanium is greater than the etch-rate of silicon; surface roughness after the washing with silicon face is applied the SC-1 washing and the time compares; comparatively coarse, this surface roughness raises along with germanium concentration and becomes big.Because along with germanium concentration is high more, the distortion of strained silicon layer increases.When germanium concentration was higher, because can increase the distortion of strained silicon layer, germanium-silicon layer is higher with germanium concentration to be good, but the surface roughness after the washing can become bigger.Make oxide-film between the centre, with this shaggy germanium-silicon layer surface and the made adhesive substrates of silicon substrate applying that becomes the matrix wafer, the adhesion of binding face reduces, for example subsequently in conjunction with the technologies such as silicon substrate filming of wafer the time, can become binding face in conjunction with bad reason, cause adhesive substrates to make output and descend.
To this; discoveries such as present inventor; after the germanium-silicon layer surface forms diaphragm; when using the 1st cleaning solution to have the mode of diaphragm to come etching to wash this diaphragm with remnants; germanium-silicon layer is protected when washing; can prevent rough surface; and; because by the etching removal a little of the 1st cleaning solution diaphragm quilt; can improve clean result; the adhesion that can prevent binding face reduces; and; by can the aforementioned diaphragm of etching; and 2nd cleaning solution littler than the 1st cleaning solution to the etch-rate of aforementioned diaphragm removes aforementioned diaphragm, so that the mode that aforementioned germanium-silicon layer exposes is when washing by the washed multilager base plate of aforementioned the 1st cleaning solution; because make by the 2nd less cleaning solution of etch-rate and germanium-silicon layer carried out etching can not produce shaggy mode; the shaggy while of germanium-silicon layer preventing to become binding face can promote clean result significantly, can prevent that the adhesion of binding face from reducing.
On the other hand, as previously mentioned, when using ion implantation to make the SOI wafer, when ion injects, make oxide-film between Si
1-XGe
XWhen between laminar surface and the base wafer it being sticked together, the binding face that has after peeling off heat treatment produces space or pore etc. in conjunction with bad problem existence.
But, in order to remove this organic substance and metal impurities, if to Si
1-XGe
XWhen laminar surface applies the SC-1 washing, based on aforementioned reason, the Si after the washing
1-XGe
XThe laminar surface roughness can become bigger, makes the Si of oxide-film after the centre makes washing
1-XGe
XWhen laminar surface and matrix wafer sticked together, binding face can produce what is called such as space or pore in conjunction with bad problem after peeling off heat treatment.
And, make the Si of oxide-film after the centre makes washing
1-XGe
XWhen laminar surface and matrix wafer stick together, improve Si
1-XGe
XDuring the Ge concentration of layer, because the lattice relaxation in the si-enriched germanium layer can't carry out fully, the crystallinity that produces transposition and the strained silicon layer directly over it is variation also.
To this, present inventor etc. find at Si
1-XGe
XThe surface of layer (0＜X＜1) forms protective layer; inject at least a hydrogen ion or noble gas ion by this protective layer, form ion implanted layer, subsequently; washing be formed with this ion implanted layer in conjunction with wafer the time, can prevent because of the Si that produced of washing by protective layer
1-XGe
XThe face of layer is coarse, can remove simultaneously to be attached to organic substance or the metal impurities that inject the surface when injecting ion, can prevent that the binding face after peeling off heat treatment from producing space or pore.And; make after this washing in conjunction with wafer protection laminar surface and matrix wafer; at dielectric films such as silicon oxide layers between the state of centre or when it is sticked together; the interface of protective layer and matrix wafer becomes and is easy to generate slip; when subsequently the surface of peel ply being carried out thermal oxidation and forms heat oxide film, can suppress Si
1-XGe
XThe germanium of layer is concentrated and the si-enriched germanium layer that forms produces transposition, can carry out lattice relaxation fully simultaneously, thereby has finished the present invention.
Below use accompanying drawing that example of the present invention is described.
Fig. 1 is the figure of an example of the washing process of multilager base plate of the present invention.
At first, shown in Fig. 1 (a), prepare to have the multilager base plate 1 of germanium-silicon layer 2 as top layer.This multilager base plate 1 is not particularly limited when using germanium-silicon layer as top layer, for example can use at the surperficial epitaxial growth germanium-silicon layer of silicon single crystal wafer and formation etc.
Then, shown in Fig. 1 (b), form diaphragm 3 on the surface of this germanium-silicon layer 2.Diaphragm 3 can be made of for example monocrystalline silicon, polysilicon, amorphous silicon, silica etc.
Then, shown in Fig. 1 (c), wash this diaphragm 3 by the 1st cleaning solution.For example multilager base plate 1 can be impregnated in the 1st cleaning solution washs.The 1st cleaning solution can etching protective film 3, and for example if diaphragm 3 is made of silicon, the 1st cleaning solution can use by NH
4OH and H
2O
2The SC-1 cleaning solution that mixed aqueous solution constituted.Because by washing, diaphragm 3 can be promoted clean result by etching a little.Described have the mode of diaphragm 3 to wash with remnants, because germanium-silicon layer 2 is protected, can prevent rough surface, can prevent that the adhesion of binding face from reducing.
At this moment, being preferably the thickness that makes remaining diaphragm 3 is that the following mode of above 100 nanometers of 1 nanometer is washed.When if thickness 1 nanometer of remaining diaphragm 3 is above, have thickness sufficient and can protect germanium-silicon layer can not cause rough surface because of washing, be in the suds can not expose and cause part surface coarse because of the part of germanium-silicon layer 2.And, if when 100 nanometers are following, in back technology by fitting with the wafer that combines that has oxide-film on the surface, when making applying SOI wafer with strained silicon layer, can make thickness extremely thin from deformation layer to oxide-film, the effect that can have abundant reduction stray capacitance (straycapacitor), this is favourable to soi structure.
At this moment, by composition or temperature or the washing time of adjusting the 1st cleaning solution, can easily adjust the thickness of remaining diaphragm 3.For example, as if the temperature that reduces cleaning solution, when shortening washing time, the etch quantity in the time of can reducing washing.By adjusting described condition, thickness that can remaining diaphragm 3 is for example below 100 nanometers more than 1 nanometer.
Fig. 2 is the figure of another one example of the washing process of multilager base plate of the present invention.Fig. 2 (a)～Fig. 2 (c) can carry out identical technology shown in Fig. 1 (a)～Fig. 1 (c).Subsequently, as Fig. 2 (d), by the 2nd cleaning solution remove by the washing of the 1st cleaning solution remaining diaphragm 3 ' with expose germanium-silicon layer 2 ' mode wash.For example can be by with multilager base plate 1 ' impregnated in the 2nd cleaning solution and wash.The 2nd cleaning solution can etching protective film 3 ', and littler than the 1st cleaning solution to the etch-rate of diaphragm, diaphragm 3 ' constitute for example by silicon, the 2nd washing lotion can use be adjusted to etch-rate than the 1st cleaning solution little by NH
4OH and H
2O
2The SC-1 cleaning solution that mixed aqueous solution constituted.Like this; remove diaphragm 3 ' make SiGe 2 ' expose by the 2nd cleaning solution; because be so that germanium-silicon layer 2 ' can not produce shaggy mode carries out the etching washing; the germanium-silicon layer 2 that can prevent to become binding face ' the shaggy while, clean result can be improved many, as can positively to prevent binding face adhesion and reduce.
The etch-rate of the 2nd cleaning solution is less than the 1st cleaning solution, when the temperature that for example makes the 2nd cleaning solution is lower than the temperature of the 1st cleaning solution, can easily reduce the etch-rate of the 2nd cleaning solution, makes it can not make germanium-silicon layer 2 ' generation rough surface.Can certainly reduce etch-rate by the composition of adjusting the 2nd cleaning solution.
Fig. 3 is the figure of the attaching process of multilager base plate of the present invention.At first, prepare to use the washed multi-layer sheet 1 of aforesaid washing methods ".Multi-layer sheet 1 " top layer 4 are germanium-silicon layers or remnants have diaphragm in the above, have and can prevent the shaggy surface of causing because of washing.And, prepare and this multilager base plate 1 " other substrate 5 (matrix wafer) of fitting.Matrix wafer 5 can be the silicon single crystal wafer that for example is formed with oxide-film on the surface, also can be insulating properties wafers such as quartz, carborundum, aluminium oxide, diamond." descend with the adhesion of binding face, any all is that to have the less surface of roughness later with washing be preferable in order to prevent multilager base plate 1.
Then, the applying multi-layer sheet 1 " with matrix wafer 5.Applying can be carried out in room temperature, subsequently in nitrogen environment, heat-treats with 200～1200 ℃ temperature and to promote adhesion." when fitting with matrix wafer 5, can prevent to reduce because of the rough surface of binding face or the adhesion that pollution caused, the technology subsequently can not produce unfavorable condition such as peels off, and helps to promote the manufacturing output of adhesive substrates to make multilager base plate 1 like this.
Fig. 4 (a)～Fig. 4 (i) is the figure of an example of the manufacturing process of bonded wafer of the present invention.At first, shown in Fig. 4 (a), by the Si of vapor growth method at about 10～500 nano thickness of the superficial growth of silicon single crystal wafer 11
1-XGe
XLayer 12.At this moment, also can make Si
1-XGe
XLayer 12 X, that is to say that Ge consists of necessarily, for example, make X=0, form when the inclination that increases gradually towards surperficial X is formed layer, can be suppressed at Si effectively at early growth period
1-XGe
XThe transposition that layer is produced.And, in order to suppress transposition, make X＜0.2 for good, X≤0.15 o'clock can suppress transposition fully.
Vapor growth method can pass through CVD (chemical vapour deposition (CVD); Chemical Vapor Depostion) or MBE (molecular beam epitaxy; Molecular Beam EpitaXy) method waits and carries out.When using the CVD method, for example can use SiH
4Or SiH
2Cl
2And GeH
4Mist.Can use H
2As carrier.It is that 600～1,000 ℃, pressure are below 100 holders (Torr) that growth conditions for example can make temperature.
Then, shown in Fig. 4 (b), Si is arranged in growth
1-XGe
XThe surface of layer 12 forms protective layer 13.Protective layer 13 can use monocrystalline silicon layer, amorphous silicon layer, polysilicon layer or silicon oxidation rete etc.Described arbitrary protective layer can use vapor growth method to form.If during protective layer silicon oxidation rete, also can form, also can be used as BOX after the applying and (imbed oxide-film by thermal oxidation; BuriedOxide) layer.And, when protective layer is monocrystalline silicon layer,, can utilize as concentrating the germanium-silicon layer that germanium forms by technology subsequently.The thickness of protective layer 13 is preferable with the thickness that can fully produce the degree of slip at binding face.For example, when protective layer 13 was the silicon oxidation rete, thickness was below 100 nanometers, being preferable below 50 nanometers.
Then, shown in Fig. 4 (c), inject at least a hydrogen ion or noble gas ion with predetermined close, form ion implanted layer 14 by aforementioned protective layer 13.At this moment, quite rely on the injection energy, can set and inject energy and make to reach and wish to inject the degree of depth because ion injects the degree of depth.And, inject the degree of depth at ion of the present invention and can reach inside in conjunction with the silicon single crystal wafer 11 of wafer, also can reach in conjunction with and Si
1-XGe
XThe interface of layer 12, or reach Si as described later
1-XGe
XThe inside of layer 12.In a word, if can make Si
1-XGe
XLayer at least a portion of 12 moved to establish to the matrix wafer and got final product as the peel ply after fitting.
And, planting son when injecting, can prevent channeling effect and can improve the inner evenness that ion injects the degree of depth with the direction of the Surface Vertical of protective layer 13, can form the second best in quality ion implanted layer 14.When particularly protective layer 13 is silicon oxidation rete, amorphous silicon layer, polysilicon layer etc., can prevent to produce channeling effect effectively.
Then, shown in Fig. 4 (d),, remove the organic substance and the metal impurities on surface by the surface that washing is washed protective layer 13 in conjunction with wafer.This washing can be identical with for example washing of diaphragm shown in the earlier figures 1 (c) (example of the washing process of multilager base plate of the present invention).Washing can be washed by the SC-1 of the common the same terms that uses of silicon wafer washing and be carried out.Also can suitably form the SC-1 washing washs (by HCl and H with SC-2
2O
2Mixed aqueous solution washing) carry out.And, also can be by (passing through H in the water washing of described washing combination sulfuric acid hydrogen peroxide
2SO
4And H
2O
2Mixed aqueous solution washing) or Ozone Water washing, can improve removal effect of organic matter.There is Si on the surface
1-XGe
XLayer 12 is when exposing, and when carrying out the common washing of silicon substrate as mentioned above, on the surface Si arranged
1-XGe
XThe surface of layer 12 can produce rough surface, and still, the present invention is by protective layer 13 protection Si
1-XGe
XLayer 12 can not produce rough surface.Therefore, can prevent that in back technology space, pore etc. are in conjunction with bad generation.
At this moment, the matrix wafer 15 to other preparation also can carry out same washing.If during matrix wafer 15 silicon single crystal wafers of this preparation etc., be formed with silicon oxide layer 16 on the surface.Because formed silicon oxide layer 16 when in the end bonded wafer is finished, can become the BOX layer, and is in order to obtain high-quality, preferable to form by thermal oxidation.And, when using insulating properties wafers such as quartz, carborundum, aluminium oxide, diamond,, also can wait to form silicon oxide layer by the CVD method though not necessarily must form silicon oxide layer 16 on the surface as matrix wafer 15.
Then, shown in Fig. 4 (e), make silicon oxide layer 16 between the centre, in room temperature with the surface of protective layer 13 and the surface mount of matrix wafer 15.As previously mentioned, if during insulating properties wafers such as matrix wafer 15 quartz, protective layer 13 and matrix wafer 15 are directly sticked together.At this moment; because protective layer 13 is with silicon oxide layer 16 or the interface of insulating properties matrix wafer 15 becomes binding face; be easy to generate slip at this binding face; pass through to form heat oxide film 18 subsequently; germanium concentration is enhanced and the si-enriched germanium layer 19 that forms can easily carry out lattice relaxation fully, can suppress to produce transposition in the si-enriched germanium layer 19.
Then, shown in Fig. 4 (f), for example ion implanted layer 14 is peeled off as parting plane by the heat treatment (peeling off heat treatment) that applies more than 500 ℃.Whereby, the silicon layer 17 and the Si of silicon single crystal wafer
1-XGe
XLayer 12 and protective layer 13 move and are located at the matrix wafer side as peel ply.
And; shown in Fig. 4 (e); by two plates is carried out plasma treatment as the face that sticks together; before the surface mount technology of surface that makes protective layer 13 and matrix wafer 15, handle; when improving tack strength; lift-off processing after needn't sticking together also can be carried out mechanicalness at ion implanted layer 14 and be peeled off.
Then, shown in Fig. 4 (g), carried out thermal oxidation and form heat oxide film 18 moving the peel ply surface of being located at the matrix wafer side.At this moment, thermal oxidation is at the silicon layer 17 and the Si of peel ply
1-XGe
XThe part of layer 12 is carried out.At this moment the Si of peel ply
1-XGe
XA layer part of 12 be during by thermal oxidation, because germanium almost is not housed in the oxide-film, exists by the germanium of thermal oxidation part to partly being moved by thermal oxidation, and form that germanium is concentrated and the si-enriched germanium layer 19 that forms.And, when protective layer 13 is monocrystalline silicon layer, also can utilize the part of the germanium-silicon layer 19 that protective layer 13 is concentrated as germanium.As mentioned above, because by oxidation Si
1-XGe
XLayer 12 germanium concentration that can improve in the si-enriched germanium layer 19, in si-enriched germanium layer 19, produce stronger distortion (compression), but because near si-enriched germanium layer 19, there is the incomplete applying of chemical bond interface, mode at its interface with the distortion that relaxes si-enriched germanium layer 19 produces slip, can the limit suppresses that si-enriched germanium layer 19 produces transpositions, lattice relaxation is reached on the limit.
At this moment, because injecting, ion damage is arranged in surperficial remnants at silicon layer 17, peel ply surface directly is easy to generate OSF when carrying out thermal oxidation than 1000 ℃ of higher temperature, with below 1000 ℃, be preferably with the temperature below 950 ℃ to come silicon layer 17 is carried out thermal oxidation, till this damage meeting is accommodated by hot oxygen rete, perhaps, be preferably release surface is ground (contact polishing a little; Touch polish) after, it is preferable carrying out thermal oxidation.
On the other hand, thermal oxidation Si
1-XGe
XLayer 12 o'clock, as previously mentioned, because germanium almost is not housed in the oxide-film, be concentrated in the si-enriched germanium layer 19 by thermal oxidation, oxidate temperature is during less than 900 ℃, separate out because be easy to generate germanium,, be preferably more than 1000 ℃ so oxidizing temperature is more than 900 ℃ at the interface of heat oxide film 18 and si-enriched germanium layer 19.And, also can by after the oxidation at Ar, H
2, N
2Etc. appending heat treatment in the non-oxidizable environment, can make the germanium diffusion, make the germanium concentration of depth direction even.
That is to say, form ion implanted layer in the inside of silicon single crystal wafer 11 and peeled off, when the peel ply surface is silicon layer 17, with below 1000 ℃, the temperature that is preferably below 950 ℃ heat-treats, the integral body of silicon layer 17 is become till the heat oxide film, subsequently, to being positioned at the Si of silicon layer 17 bottoms
1-XGe
XLayer 12 is when carrying out thermal oxidation, with more than 900 ℃, be preferably carry out oxidation more than 1000 ℃ technology for being fit to.
Then, shown in Fig. 4 (h), remove formed heat oxide film 18 the si-enriched germanium layer 19 of lattice relaxation is exposed.Can use the HF aqueous solution to remove heat oxide film.
At last, shown in Fig. 4 (i),, carry out epitaxial growth monocrystalline silicon layer 20 by the surface of vapor growth method at the si-enriched germanium layer 19 that exposes.Epitaxial growth can wait by CVD method or MBE method to be carried out.During the CVD method, for example, can use SiH
4Or SiH
2Cl
2As raw material.Growth conditions can be temperature 600～1, below 100 holders of 000 ℃, pressure.The monocrystalline silicon layer 20 of being grown by with the difference of the lattice constant of the si-enriched germanium layer 19 that is positioned at its lower floor, become the strained silicon layer that there is stretcher strain the inherence.Because on the few the second best in quality si-enriched germanium layer 19 of transposition, form, so become the second best in quality strained silicon layer.In order to ensure making effectively distortion, the processability when element is made, and quality, the thickness of epitaxially grown monocrystalline silicon layer 20 is preferable about with 10～50 nanometers.
Then, Fig. 5 (a)～Fig. 5 (i) is the figure of another one example of the technology of bonded wafer of the present invention.The silicon single crystal wafer 11 of Fig. 5 (a), Fig. 5 (b) ' the surface form Si
1-XGe
XLayer 12 ' and protective layer 13 ', can be undertaken by Fig. 4 (a), Fig. 4 (b) same process.
Then, shown in Fig. 5 (c), by aforementioned protective layer 13 ' inject a kind of hydrogen ion or noble gas ion of predetermined close at least, at Si
1-XGe
XLayer 12 ' inside form ion implanted layer 14 '.At this moment, also can be at Si
1-XGe
XLayer 12 ' with silicon single crystal wafer 11 ' interface formation ion implanted layer 14 '.Inject the energy size because the degree of depth of ion implanted layer depends on,, reach the injection degree of depth of hope so can set the injection energy.
Then, shown in Fig. 5 (d), Fig. 5 (e), the washing protective layer 13 ' the surface remove the surface organic substance or metal impurities.This washing also can be used washing agent identical when washing diaphragm shown in the earlier figures 1 (c).Also to the identical washing of the matrix wafer 15 of other preparation ' carry out.Then, make silicon oxide layer 16 ' between the centre, with diaphragm 13 ' the surface and matrix wafer 15 ' the surface directly stick together in room temperature.Described technology can be used with Fig. 4 (d), Fig. 4 (e) same process and carry out.
Then, shown in Fig. 5 (f), for example, by the heat treatment (lift-off processing) that applies temperature more than 500 ℃, with ion implanted layer 14 ' be that parting plane is peeled off.Whereby, Si
1-XGe
XThe part of layer or whole 17 ' and protective layer 13 ' quilt move and establish to the matrix wafer side.And; at this moment; also by two plates is carried out plasma treatment as the face that sticks together; as make protective layer 13 ' the surface and matrix wafer 15 ' surface mount technology before handle; when improving tack strength; lift-off processing after needn't sticking together also can be at ion implanted layer 14 ' carry out mechanicalness to peel off.
Then, shown in Fig. 5 (g), to being moved the Si that is located at the matrix wafer side
1-XGe
XThe layer 17 ' surface carry out thermal oxidation form heat oxide film 18 '.At this moment, by heat oxide film 18 ' formation, germanium is concentrated and the si-enriched germanium layer 19 that forms '.And, protective layer 13 ' when being monocrystalline silicon layer, also can utilize the germanium-silicon layer 19 of protective layer 13 ' be concentrated as germanium ' a part.In the stronger distortion (compression) of si-enriched germanium layer 19 ' middle generation, but because si-enriched germanium layer 19 ' near exist the applying interface, this at the interface with relax si-enriched germanium layer 19 ' the mode of distortion produce slip, and can suppress si-enriched germanium layer 19 ' generation transposition and reach lattice relaxation.
At this moment, as previously mentioned, because germanium almost is not housed in the oxide-film, by thermal oxidation be concentrated in si-enriched germanium layer 19 ' in, because oxidate temperature is during less than 900 ℃, heat oxide film 18 ' with si-enriched germanium layer 19 ' the interface be easy to generate germanium and separate out, therefore make oxidizing temperature more than 900 ℃, be preferably more than 1000 ℃ for preferable.
And, to moving the Si that establishes
1-XGe
XThe layer 17 ' affected layer contact polishing after, be preferably the Si that establishes moving
1-XGe
XLayer 17 ', with oxidizing temperature more than 900 ℃, be preferably 1000 ℃ with on carry out germanium and concentrate.At this moment, because the surface of peel ply is not a silicon layer, can not produce the problem of OSF, the heat treatment of carrying out at once more than 1000 ℃ does not have obstruction yet.
Then, shown in Fig. 5 (h), remove the si-enriched germanium layer 19 of formed heat oxide film 18 ' expose lattice relaxation '.Removal heat oxide film 18 ' can use the HF aqueous solution.
And, last, shown in Fig. 5 (i), by vapor growth method the si-enriched germanium layer 19 that exposes ' surperficial epitaxial growth monocrystalline silicon layer 20 '.Like this monocrystalline silicon layer 20 of Xing Chenging ', by the si-enriched germanium layer 19 of its lower floor ' with the difference of lattice constant, become the strained silicon layer that there is stretcher strain the inherence.Because the few the second best in quality si-enriched germanium layer 19 of transposition ' on form, so become the second best in quality strained silicon layer.In order to ensure making effectively distortion, the processability when element is made, and quality, epitaxially grown monocrystalline silicon layer 20 ' thickness be preferable about with 10～50 nanometers.
Below, by embodiments of the invention and comparative example, specifically describe the present invention, described but the present invention is not limited to.
(embodiment 1,2, comparative example 1～3)
Surface (mirror ultrafinish face) at the silicon single crystal wafer of 200 millimeters of diameters; pile up concentration 5% shown in the following table 1 or 15% germanium-silicon layer by epitaxy; make it as top layer thing (comparative example 1,2); and then pile up the protection silicon of 20 nanometer degree as diaphragm by epitaxy in the above; make it as top layer thing (embodiment 1,2), make and amount to 4 kinds sample wafer.And, prepare not form the common minute surface silicon single crystal wafer of above-mentioned epitaxial loayer as reference usefulness.
Surface and the single crystal silicon substrate wafer of preparing in addition (heat oxide film) to the top layer of described 5 kinds sample wafer with thickness 400 nanometers, carry out the SC-1 washing with following condition, fit in room temperature, 350 ℃ carry out 2 hours heat treatment (in the nitrogen environment) afterwards, estimate surface energy with the proportional binding face of adhesion by the razor insertion.
[table 1]
| Germanium-silicon layer (50 nanometer) | Protection silicon layer (20 nanometer) | Chip architecture (from the surface) | |
| Embodiment 1 | Have: germanium 5% | Have | Protection silicon/SiGe/ |
| Embodiment | |||
| 2 | Have: | Have | Protection silicon/SiGe/Si wafer |
| Comparative example 1 | Have: germanium 5% | Do not have | The SiGe/Si wafer |
| Comparative example 2 | Have: | Do not have | The SiGe/Si wafer |
| Comparative example 3 | Do not have | Do not have | Silicon wafer |
＜SC-1 wash conditions 〉
Form: 29wt%NH
4OH:30wt%H
2O
2: H
2O=1: 1.5 (Capacity Ratio)
Liquid temperature: 80 ℃
Washing time: 3 minutes
By AFM (atomic force microscope: Atomic Force Microscope) measure near 1 micron square of the superficial layer the central part of each the sample wafer after the SC-1 washing, the RMS value (root mean square of 10 microns tetragonal surface roughnesses; Root Mean Square), and the result of the surface energy when measuring each sample wafer with the applying of matrix wafer by the razor insertion, as table 2 and shown in Figure 6.And, before and after SC-1 washing, measure the film thickness on the top layer of sample wafer, calculate the etch quantity of washing to top layer, the result is as shown in table 3.
[table 2]
| Surface roughness after the washing (RMS value) (nanometer) | Surface energy (J/m2) | ||
| 1 micron square | 10 microns squares | ||
| Embodiment 1 | 0.129 | 0.087 | 1.949 |
| | 0.144 | 0.087 | 1.9 |
| Comparative example 1 | 0.157 | 0.103 | 1.777 |
| Comparative example 2 | 0.209 | 0.121 | 1.578 |
| Comparative example 3 | - | - | 1.911 |
[table 3]
| Skin covering of the surface thickness (nanometer) | Etch quantity (nanometer) | ||
| Before the washing | After the washing | ||
| Embodiment 1 | 18.93 | 17.39 | 1.54 |
| | 20.53 | 18.72 | 1.81 |
| Comparative example 1 | 46.43 | 43.99 | 2.44 |
| Comparative example 2 | 50.11 | 45.23 | 4.88 |
As shown in table 2, aspect the surface roughness after washing, with respect to the value of comparative example 1,2, the value of embodiment 1,2 is less, and when for example making comparisons with germanium concentration 15%, 1 micron tetragonal RMS value of embodiment 2 is 0.144 nanometer, but comparative example 2 is 0.209 nanometer, differs greatly.Result thus learns that implementing 1,2 can prevent to become coarse because of washing causes top layer.And about surface energy, as table 2 and shown in Figure 6, relatively the time, the value of embodiment 1,2 is bigger with the value of comparative example 1,2, for example with respect to the 1.578J/m of comparative example 2
2, embodiment 2 is 1.9J/m
2, the value during with the no germanium-silicon layer of comparative example 3 is 1.911J/m
2Same good.The result learns can prevent to descend because of washing causes the adhesion of binding face thus.
And as shown in table 3, even same wash conditions, relatively the time, the etch quantity of embodiment 1,2 is less with comparative example 1,2, and can the confirmation form surface roughness bigger its etch-rate of sample is higher.
(embodiment 3, comparative example 4)
Use shown in the table 1 with the made sample wafer (embodiment 3) of embodiment 2 the same terms, use and the made sample wafer (comparative example 4) of comparative example 2 the same terms, the liquid temperature that only changes aforementioned SC-1 wash conditions is 25 ℃, 50 ℃, 80 ℃ and carries out SC-1 washing, relatively the etch quantity on the top layer of each sample wafer.Result such as table 4 and shown in Figure 7.Can learn that from table 4 and Fig. 7 in arbitrary liquid temperature, when comparing with comparative example 4, the etch quantity of embodiment 3 is less, and along with the liquid temperature increases, it is big that both difference becomes.And, can confirm can reduce etch quantity by reducing the liquid temperature of SC-1 cleaning solution, can adjust etch quantity by adjusting the liquid temperature.
[table 4]
| Etch quantity (nanometer) | |||
| 25℃ | 50℃ | 80 | |
| Embodiment | |||
| 3 | 0.06 | 0.41 | 1.81 |
| Comparative example 4 | 0.09 | 1.01 | 4.88 |
Then; to the sample wafer of embodiment 2 (the protection silicon layer: 20 nanometers) carry out the SC-1 washing 10 minutes of liquid temperature 80 degree, the silicon layer of skin section is removed about 18 nanometers after, follow; carry out germanium-silicon layer being exposed than its more SC-1 washing 6 minutes of 50 ℃ of the liquid temperature of low temperature.Similarly measure the surface roughness of the germanium-silicon layer expose with embodiment 1,2 by AFM.And, measure surface energy by embodiment 1,2 same procedure.As a result, surface roughness is in 1 micron square, 10 microns squares respectively do for oneself 0.15 nanometer, 0.09 nanometer.And surface energy is 1.88J/m
2, obtain about equal good result with embodiment.
(embodiment 4)
On the surface of the silicon single crystal wafer of 200 millimeters of diameters, by the grow Si of about 150 nanometers of CVD method
0.97Ge
0.03Layer (X=0.03) is by the monocrystalline silicon protective layer of CVD method in its surface formation 50 nanometers.By this monocrystalline silicon protective layer with hydrogen ion (H
+) the injection energy is 40keV, dosage 5 * 10
16Atoms/cm
2Condition inject ion, form ion implanted layer on silicon wafer single crystals protective layer surface.After hydrogen ion injects,, carried out sulfuric acid hydrogen peroxide cleaning 5 minutes with 120 ℃, then, carry out SC-1 washing 3 minutes with 80 ℃ to monocrystalline silicon protective layer surface.Then; itself and the single crystal silicon substrate wafer that washed, has the hot oxygen film of 400 nanometers with the same terms are at room temperature sticked together; peeled off heat treatment 30 minutes with 500 ℃ under ar gas environment, peel off at the place at ion implanted layer, makes monocrystalline silicon protective layer and Si
0.97Ge
0.03The part of layer and silicon layer moves to the matrix wafer side.Then, carry out thermal oxidation with 950 ℃, make the silicon layer thermal oxidation after, then temperature is increased to 1100 ℃, by making Si
0.97Ge
0.03A part of thermal oxidation of layer forms germanium concentration and is the si-enriched germanium layer more than 20%.Subsequently, remove oxide-film, the si-enriched germanium layer is exposed, by the silicon layer of CVD method in its surperficial epitaxial growth 50 nano thickness degree by the 5%HF aqueous solution.
Prepare 20 bonded wafers of making like this, the number of space and pore is calculated on visual surface, and space and stoma number that the average wafer of result is produced are about 0.5.
(embodiment 5)
On the surface of the silicon single crystal wafer of 200 millimeters of diameters, by the grow Si of about 150 nanometers of CVD method
0.97Ge
0.03Layer (X=0.03) is by the amorphous silicon protective layer of CVD method in its surface formation 50 nanometers.By this amorphous silicon protective layer with hydrogen ion (H
+) the injection energy is 40keV, dosage 5 * 10
16Atoms/cm
2Condition inject ion, form ion implanted layer on amorphous silicon protective layer surface.After hydrogen ion injects,, carry out successively carrying out SC-1 washing 3 minutes, carrying out SC-2 washing 3 minutes, carry out SC-1 washing 3 minutes with 80 ℃ with 80 ℃ with 80 ℃ to amorphous silicon protective layer surface.Then; itself and the single crystal silicon substrate wafer that washed, has the hot oxygen film of 400 nanometers with the same terms are at room temperature sticked together; peeled off heat treatment 30 minutes with 500 ℃ under ar gas environment, peel off at the place at ion implanted layer, makes amorphous silicon protective layer and Si
0.97Ge
0.03The part of layer is moved and is established to the matrix wafer side.Then, carry out thermal oxidation with 950 ℃, make the silicon layer thermal oxidation after, then temperature is increased to 1100 ℃, by making Si
0.97Ge
0.03A part of thermal oxidation of layer forms germanium concentration and is the si-enriched germanium layer more than 20%.Subsequently, remove oxide-film, the si-enriched germanium layer is exposed, by the silicon layer of CVD method in its surperficial epitaxial growth 50 nano thickness degree by the 5%HF aqueous solution.
Prepare 20 bonded wafers of making like this, the number of space and pore is calculated on visual surface, and space and stoma number that the average wafer of result is produced are about 0.8.
(embodiment 6)
On the surface of the silicon single crystal wafer of 200 millimeters of diameters, by the grow Si of about 150 nanometers of CVD method
0.97Ge
0.03Layer (X=0.03) is by the monocrystalline silicon protective layer of CVD method in its surface formation 50 nanometers.By this monocrystalline silicon protective layer with hydrogen ion (H
+) the injection energy is 15keV, dosage 5 * 10
16Atoms/cm
2Condition inject ion, at Si
0.97Ge
0.03The inside of layer forms ion implanted layer.After hydrogen ion injects,, carry out the sulfuric acid aquae hydrogenii dioxidi with 120 ℃ and clean 5 minutes, then, carry out SC-1 washing 3 minutes with 80 ℃ to monocrystalline silicon protective layer surface.Then; itself and the single crystal silicon substrate wafer that washed, has the hot oxygen film of 400 nanometers with the same terms are at room temperature sticked together; peeled off heat treatment 30 minutes with 500 ℃ under ar gas environment, peel off at the place at ion implanted layer, makes amorphous silicon protective layer and Si
0.97Ge
0.03The part of layer moves to the matrix wafer side.Then, carry out thermal oxidation with 1100 ℃, make Si
0.97Ge
0.03A part of thermal oxidation of layer forms germanium concentration and is the si-enriched germanium layer more than 20%.Subsequently, remove oxide-film, the si-enriched germanium layer is exposed, by the silicon layer of CVD method in its surperficial epitaxial growth 50 nano thickness degree by the 5%HF aqueous solution.
Prepare 20 bonded wafers of making like this, the number of space and pore is calculated on visual surface, and space and stoma number that the average wafer of result is produced are about 0.5.
(comparative example 5)
On the surface of the silicon single crystal wafer of 200 millimeters of diameters, by the grow Si of about 150 nanometers of CVD method
0.97Ge
0.03Layer (X=0.03) is by the monocrystalline silicon protective layer of CVD method in its surface formation 50 nanometers.By this Si
0.97Ge
0.03Layer is with hydrogen ion (H
+) the injection energy is 40keV, dosage 5 * 10
16Atoms/cm
2Condition inject ion, at Si
0.97Ge
0.03The top layer of layer forms ion implanted layer.After hydrogen ion injects,, carried out sulfuric acid hydrogen peroxide cleaning 5 minutes with 120 ℃, then, carry out SC-1 washing 3 minutes with 80 ℃ to monocrystalline silicon protective layer surface.Then, itself and the single crystal silicon substrate wafer that washed, has the hot oxygen film of 400 nanometers with the same terms are at room temperature sticked together, peeled off heat treatment 30 minutes with 500 ℃ under ar gas environment, peel off at the place at ion implanted layer, makes Si
0.97Ge
0.03The part of layer and silicon layer moves to the matrix wafer side.Then, anneal with 1200 ℃, improve bond strength and make flattening surface simultaneously.
Prepare 20 bonded wafers of making like this, the number of space and pore is calculated on visual surface, and space and stoma number that the average wafer of result is produced are about 8.
That is to say that according to the bonded wafer of manufacturing of the present invention, the space and the stoma number that are produced are less, effect of the present invention obtains confirming.
And the present invention is not limited to the foregoing description.The foregoing description is exemplary, has the identical in fact formation of being put down in writing with claims scope of the present invention of technological thought, the technology that reaches effect same, all should be included in the scope of claims of the present invention.
Claims (16)
1. the washing methods of a multilager base plate; at least have the washing methods of germanium-silicon layer as the multilager base plate on top layer; wherein form diaphragm at least on the surface of this germanium-silicon layer, the 1st cleaning solution by can this diaphragm of etching has the method for this diaphragm to wash this multilager base plate with remnants subsequently.
2. the washing methods of multilager base plate as claimed in claim 1 wherein by adjusting composition, temperature or the washing time of the 1st cleaning solution, is adjusted the thickness of this remnants diaphragm.
3. the washing methods of multilager base plate as claimed in claim 1 or 2, wherein, so that thickness that should the remnants diaphragm is that the mode that 1 nanometer is above, 100 nanometers are following is washed.
4. as the washing methods of each described multilager base plate in the claim 1 to 3, wherein this diaphragm is made of silicon, and the 1st cleaning solution is by NH
4OH and H
2O
2Mixed aqueous solution constitute.
5. as the washing methods of each described multilager base plate in the claim 1 to 4; wherein by a kind of can this diaphragm of etching and the etch-rate of this diaphragm 2nd cleaning solution littler than the 1st cleaning solution removed this diaphragm so that the mode that this germanium-silicon layer exposes is washed through the washed multilager base plate of the 1st cleaning solution.
6. the washing methods of multilager base plate as claimed in claim 5, wherein the 2nd cleaning solution is by NH
4OH and H
2O
2Mixed aqueous solution constitute.
7. as the washing methods of claim 5 or 6 described multilager base plates, wherein the temperature of the 2nd cleaning solution is lower than the temperature of the 1st cleaning solution.
8. the applying method of a substrate; make through as the germanium-silicon layer on the top layer of the washed multilager base plate of each described multilager base plate washing methods in the claim 1 to 7 institute or the surface of diaphragm, with direct or make the surface applying of the intervenient mode of dielectric film and other substrate.
9. the manufacture method of a bonded wafer comprises following steps: form Si on this surface in conjunction with the silicon single crystal wafer of wafer at least
1-XGe
XLayer (0＜X＜1); At this Si
1-XGe
XThe surface of layer forms protective layer; Plant by one of them that sees through that this protective layer injects hydrogen ion or noble gas ion and to form ion implanted layer; Washing be formed with this ion implanted layer this in conjunction with wafer; With after this washing in conjunction with the protective layer surface of wafer with directly or oxide-film is sticked together between the mode and the matrix wafer of centre, peel off from this ion implanted layer subsequently; To carrying out thermal oxidation, form heat oxide film because of above-mentioned surface of peeling off the peel ply that moves to the matrix wafer side; The si-enriched germanium layer that germanium is concentrated by the heat oxide film of removing this formation exposes; Make the surperficial epitaxial growth monocrystalline silicon layer of this si-enriched germanium layer that exposes.
10. the manufacture method of bonded wafer as claimed in claim 9, wherein this X is less than 0.2.
11., wherein use at least a this protective layer that is used as in monocrystalline silicon layer, amorphous silicon layer, polysilicon layer or the silicon oxidation rete as the manufacture method of claim 9 or 10 described bonded wafers.
12. as the manufacture method of each described bonded wafer in the claim 9 to 11, wherein this ion injects and carries out with the direction vertical with this protective layer.
13. as the manufacture method of each described bonded wafer in the claim 9 to 12, wherein during sticking together with this matrix wafer after this washing in conjunction with the protective layer of wafer surface between wherein dielectric film, only be formed at the surface of this matrix wafer.
14., wherein use silicon single crystal wafer or insulating properties wafer as this matrix wafer as the manufacture method of each described bonded wafer in the claim 9 to 13.
15. as the manufacture method of each described bonded wafer in the claim 9 to 14, wherein the temperature of this peel ply surface of thermal oxidation when concentrating the germanium of this germanium-silicon layer is more than 900 ℃.
16. as the manufacture method of each described bonded wafer in the claim 9 to 15, wherein this peel ply of thermal oxidation surface is so that the temperature of silicon layer that should the surface when becoming heat oxide film is below 1000 ℃.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP318040/2003 | 2003-09-10 | ||
| JP318078/2003 | 2003-09-10 | ||
| JP2003318040A JP4370862B2 (en) | 2003-09-10 | 2003-09-10 | Laminated substrate cleaning method and substrate laminating method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1849700A true CN1849700A (en) | 2006-10-18 |
| CN100550312C CN100550312C (en) | 2009-10-14 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004800260982A Active CN100550312C (en) | 2003-09-10 | 2004-09-07 | The manufacture method of the washing methods of multilager base plate and the applying method of substrate and bonded wafer |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP4370862B2 (en) |
| CN (1) | CN100550312C (en) |
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- 2003-09-10 JP JP2003318040A patent/JP4370862B2/en not_active Expired - Lifetime
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Also Published As
| Publication number | Publication date |
|---|---|
| CN100550312C (en) | 2009-10-14 |
| JP2005082870A (en) | 2005-03-31 |
| JP4370862B2 (en) | 2009-11-25 |
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