CN108766873A - Method for permanent engagement chip - Google Patents

Method for permanent engagement chip Download PDF

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Publication number
CN108766873A
CN108766873A CN201810604777.7A CN201810604777A CN108766873A CN 108766873 A CN108766873 A CN 108766873A CN 201810604777 A CN201810604777 A CN 201810604777A CN 108766873 A CN108766873 A CN 108766873A
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China
Prior art keywords
contact surface
hopper
starting material
substrate
conversion zone
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CN201810604777.7A
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CN108766873B (en
Inventor
T.普拉赫
K.欣格尔
M.温普林格
C.弗勒特根
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EV Group E Thallner GmbH
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EV Group E Thallner GmbH
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    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
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    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
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    • H01L21/762—Dielectric regions, e.g. EPIC dielectric isolation, LOCOS; Trench refilling techniques, SOI technology, use of channel stoppers
    • H01L21/7624—Dielectric regions, e.g. EPIC dielectric isolation, LOCOS; Trench refilling techniques, SOI technology, use of channel stoppers using semiconductor on insulator [SOI] technology
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Abstract

The present invention relates to the methods for permanent engagement chip.In particular it relates to which the method that the first contact surface (3) of first substrate (1) is bonded to the second contact surface (4) of second substrate (2), this method have steps of：Hopper (5) is formed in the superficial layer (6) of first contact surface (3), wherein pore size distribution increases with thickness and reduces and go to zero, the hopper (5) is at least partly filled with the first starting material or first group of starting material ,-so that the first contact surface (3) is contacted with the second contact surface (4) to form pre- engagement connection.

Description

Method for permanent engagement chip
Present patent application is application No. is 201180065964.9, and the applying date is on January 25th, 2011, with the female case Shen of topic Divisional application please.
Technical field
The present invention relates to a kind of as described in claim 1 for the first contact surface of first substrate to be bonded to second The method of second contact surface of substrate.
Background technology
The purpose of the permanent or irreversible engagement of substrate is, is generated between two contact surfaces of substrate as strong as possible And especially irreversible connection, i.e., strong engaging force.There is various measures and manufacturing method in the prior art thus.
Well known manufacturing method and the measure used till today frequently result in cannot reproduce or reproducibility difference and it is special It is the result for the condition that can hardly be applied to change.Manufacturing method especially used at present usually uses high temperature, especially> 400 DEG C of high temperature, to ensure repeatable result.
If high energy consumption and the technical issues of may damaging existing structure on substrate are by so far for high bonding force institute It is far above caused by 300 DEG C to the high-temperature part needed.
Others require to be：
Front end of line compatibility.
It is defined as the technical process compatibility during manufacturing electrically active component.Therefore it must design and engage in this way Journey：So that the live components being already present on structured wafer such as transistor neither affect adversely during the process nor It is damaged.Compatibility standard include mainly the purity (mainly in CMOS structure) of certain chemical elements, machinery can load, It can load especially by machinery caused by thermal stress.
Low stain
Not applied force.
Engaging force, which reduces, leads to more handling with caution and thus causing to break caused by direct mechanical load for structured wafer Bad probability reduces.
Invention content
Therefore, the purpose of the present invention is to design a kind of permanently connecing with high bonding force as far as possible for carefully production The method of conjunction.
This purpose is obtained using the feature of claim 1.The advantageous hair of the present invention is given in dependent claims Exhibition.Whole combinations of at least two features provided in specification, claims and/or attached drawing also fall into the frame of the present invention It is interior.In given numberical range, the numerical value in prescribed limit will also be disclosed as boundary value and can be required with any combinations Protection.
According to the first aspect of the invention, the first contact surface (3) of first substrate (1) is bonded to second substrate (2) The second contact surface (4) method, this method has steps of, and especially has following sequence：
Hopper (5) is formed in the superficial layer (6) of the first contact surface (3),
The hopper (5) is at least partly filled with the first starting material or first group of starting material,
So that the first contact surface (3) is contacted with the second contact surface (4) and connected with forming pre- engagement,
Permanent engagement is formed between first and second contact surface (3,4), by making the first starting material and the second base The second starting material contained in the conversion zone (7) of plate (2) reacts at least partly to strengthen the permanent engagement.
2. such as the method for first aspect, wherein the formation of the permanent engagement and/or reinforcing are by spreading the first starting material It is carried out in conversion zone (7).
3. such as the method for any preceding aspect, the formation of the wherein permanent engagement is happened between room temperature and 200 DEG C At a temperature of, especially during most 12 days, preferably up to 1 day, more preferably up to one hour and most preferably up to 15 minutes.
4. such as the method for any preceding aspect, wherein the irreversible engagement, which has, is more than 1.5 J/m2, especially greater than 2 J/ m2, preferably greater than 2.5 J/m2Bond strength.
5. such as the method for any preceding aspect, wherein during the reaction, molal volume that being formed has, which is more than, is reacting The reaction product (10) of the molal volume of the second starting material in layer (7).
6. such as the method for any preceding aspect, wherein the hopper (5) is formed by plasma-activated effect.
7. such as the method for any preceding aspect, wherein by the way that the tetraethoxy-silicane alkoxide layer of especially compression is used as Superficial layer (6) and form hopper (5).
8. as any preceding aspect method, wherein superficial layer (6) mainly by, especially substantially completely by especially without calmly The material of shape, especially by thermal oxidation generate silica form, and conversion zone (7) by oxidizable material, especially Be mainly by, be preferably substantially made of completely Si, Ge, InP, GaP or GaN.
9. such as the method for any preceding aspect, wherein there are grown layers between the second contact surface (4) and conversion zone (7) (8), the grown layers especially mainly formed by native silicon dioxide.
10. such as the method for previous aspect, wherein before forming permanent engagement, grown layers (8) have between 1 angstrom and 10nm Between average thickness A.
11. such as the method for any preceding aspect, wherein hopper is to be formed under vacuum.
12. one or more in the step of such as method of any preceding aspect, wherein the hopper is by being set forth below A filling：
First contact surface (3) is exposed in air, in the air especially with hyperoxia and/or water content,
By the first contact surface (3) be exposed to especially mainly by, preferably almost by especially deionized H2O and/or H2O2The fluid of composition,
First contact surface (3), which is exposed to, especially has the N of the ion energy within the scope of 0 to 200 eV2Gas and/ Or O2Gas and/or Ar gas and/or especially by 95% Ar and 5% H2The formation gas of composition.
13. as any preceding aspect method, the wherein hopper (5) be between 0.1nm and 25nm, especially Average thickness (R) formation between 0.1nm and 20nm.
14. such as the method for any preceding aspect, wherein just hopper (5) and conversion zone (7) before forming permanent engagement Between average distance (B) between 0.1nm and 15nm, especially between 0.5nm and 5nm, be more preferably between Between 0.5nm and 3nm.
15. as any preceding aspect method, wherein this it is irreversible engagement have for 2 times of pre- bond strength, preferably 4 times, More preferable 10 times, most preferably 25 times of bond strength.
The present invention basic concept be it is a kind of substrate it is at least one it is upper setting for receive the first starting material（Edukt） Hopper, first starting material contact between the substrate or generated between the substrate after interim engagement be present in The second starting material in another substrate reacts and thus forms irreversible or permanent engagement between the substrate.It is this It is formed before or after hopper in a superficial layer in first contact surface, usually especially by rinsing step to the base Plate or two substrates are cleaned.This cleaning should usually can ensure that there is no can lead to the micro- of non-junction on the surface Grain.A kind of engineering feasibility is formed to generate interim or reversible connect by the starting material contained in the hopper and the hopper Induce the reaction strengthened the permanent engagement and increase engaging speed after closing in a controlled manner directly in the contact surface, especially It is so that at least one of described contact surface is deformed by the reaction, preferably the contact surface opposite with the hopper.
For for generating the interim or pre- engagement step of reversible engagement between the substrates, for connecing in the substrate It generates weak interaction between tactile surface and there is a possibility that various.Pre- bond strength is less than permanent engagement intensity at least 2 to 3 Times, especially 5 times, more preferably 15 times, more preferable 25 times.There to be substantially 100 mJ/m2The hydrophilic pure silicon of disactivation and have Substantially 200 to 300 mJ/m2Plasma-activated hydrophilic pure silicon pre- bond strength as standard.Molecule soaks substrate Between pre- engagement be mainly due between the molecule of different chips side Van der Waals force interaction.Therefore there is permanent dipole The molecule of square is adapted to carry out the pre- engagement between chip.Property for example and not limitation using following compound as interconnection agent （Verbindungsmittel）
Water
Thio-alcohol
- AP3000
Silanes and/or
Silanol.
Suitable substrate according to the present invention for its material can be reacted with the starting material of another supply as starting material with It forms the product with higher molal volume and thus forms those of grown layers substrate on the substrate.Combining below especially has Profit, wherein the arrow left side are starting material, are then the product on the right of arrow, without indicating the confession reacted with starting material in detail The starting material or by-product answered：
- Si→SiO2、Si3N4、SiNxOy
- Ge→GeO2、Ge3N4
- α-Sn→SnO2
- B→B2O3、BN
- Se→SeO2
- Te→TeO2、TeO3
- Mg→MgO、Mg3N2
- Al→Al2O3、AlN
- Ti→TiO2、TiN
- V→V2O5
- Mn→MnO、MnO2、Mn2O3、Mn2O7、Mn3O4
- Fe→FeO、Fe2O3、Fe3O4
- Co→CoO、Co3O4
- Ni→NiO、Ni2O3
- Cu→CuO、Cu2O、Cu3N
- Zn→ZnO
- Cr→CrN、Cr23C6、Cr3C、Cr7C3、Cr3C2
- Mo→Mo3C2
- Ti→TiC
- Nb→Nb4C3
- Ta→Ta4C3
- Zr→ZrC
- Hf→HfC
- V→V4C3、VC
- W→W2C、WC
- Fe→Fe3C、Fe7C3、Fe2C。
It is also contemplated that using the semiconductor of following mixed form as substrate：
- III-V：GaP,GaAs,InP,InSb,InAs,GaSb,GaN,AlN,InN,AlxGaI-xAs、InxGaI-xN
- IV-IV：SiC,SiGe
- III-IV：InAlP
Device for non-linear optical：LiNbO3、LiTaO3、KDP (KH2PO4)
Solar cell：CdS,CdSe,CdTe,CuInSe2、CuInGaSe2、CuInS2、CuInGaS2
Conductive oxide：In2-xSnxO3-y。
According to the present invention, in at least one upper of chip and more precisely directly there are a reservoirs in respective contact surface The starting material of slot, a certain amount of at least one supply for volume expansion reaction can be stored in wherein.Therefore, starting material can be (for example) O2、O3、H2O、N2、NH3、H2O2Etc..It due to expansion, is especially expanded caused by oxide growth, based on reaction ginseng The trend for reducing system capacity with object, possible gap, hole and cavity minimize and by making these areas between making contact surface The distance between substrate in domain narrows and correspondingly increases engaging force.In the far more likely case, existing gap, hole and cavity It is closed completely so that entire engagement surface increases and correspondingly increases engaging force thus according to the present invention.
Contact surface usually secondary roughness (R of the display with 0.2nmq) roughness.This corresponds within the scope of 1nm Surface peak to peak (peak-to-peak) value.These empirical values are measured using atomic force microscope (AFM).
Reaction is suitable for the routine wafer for the Circular wafer with 200 to 300mm diameter as described in the present invention Surface is using the water of 1 monolayer (ML) to allow grown layers growth 0.1 to 0.3nm.
Therefore, it according to the present invention, specifically provides at least 2 ML, preferably at least 5 ML, even more desirably at least 10 ML Fluid, especially water is stored in hopper.
It is especially preferred by being exposed to formation hopper in plasma, this is because in addition plasma exposure is drawn Play that contact surface is smooth and hydrophiling as synergistic effect.Make the smooth surface mainly by this by plasma-activated by The viscous flow of the material of superficial layer is implemented.Hydrophilic enhancing is in particular according to following reaction particularly by the increasing of silicone hydroxyl compound Add, is preferably occurred by the Si-O compounds such as Si-O-Si that cracking is present on the surface：
Si-O-Si+H2O↔2SiOH。
Another side effect (especially because above-mentioned effect) is that pre- bond strength especially enhances 2 to 3 times.
The hopper in superficial layer in first contact surface of the first substrate has for example been applied by plasma-activated It is covered with the first substrate of thermal oxide and is formed.The gas ions activation carries out so as to adjust the ion in a vacuum chamber Condition needed for body.According to the present invention, use ion energy in the range of 0 to 2000 eV plasma release N2Gas, O2Thus gas or argon gas generate hopper, the depth on the surface (in this case, first contact surface) of the wherein processing Degree is up to 20nm, preferably up to 15nm, more preferably up to 10nm, most preferably up to 5nm.According to the present invention, it can be used and be suitble to Generate each particle type (atom and/or molecule) of the hopper.Preferably, using hopper of the generation with required property Those of atom and/or molecule.Relevant nature is mainly pore size, pore size distribution and hole density.Alternatively, according to the present invention, can make With admixture of gas, all such as (e.g.) air or by 95% Ar and 5% H2The formation gas of composition.According to used gas, Following ion is particularly present in the hopper during corona treatment：N+,N2+、O+、O2+,Ar+.First starting material It can be contained in the free space not occupied.
The hopper is formed based on considered below：Pore size is less than 10nm, preferably smaller than 5nm, more preferably less than 1nm, even more preferably less than 0.5nm, more preferably less than 0.2nm.
Hole density is more preferably directly directly proportional to the density for the particle for generating hole by effect of impact, most preferably even can be with The partial pressure of rammer and change, and the processing time of plasma system used in particularly depending on and parameter.
Preferably, the parameter in these several regions in preferred flat-top shape region (see Fig. 7) is overlapped in by variation, Pore size distribution has at least one maximum hole concentrated area in the lower face.The pore size distribution increases with thickness and reduces and tend to Zero.During shock, the region near the surface has the hole density no better than the hole density near the surface.In plasma After body processing terminates, the hole density on the surface can reduce due to stress relaxation mechanism.The pore size distribution phase of through-thickness For the surface with steep sides and relative to whole with side that is relatively flat but continuing to decline (see Fig. 7).
For pore size, pore size distribution and hole density, similar consideration is suitable for the whole side that non-used plasma generates Method.
The hopper can be by pointedly designing using with combined process parameter.Fig. 7 is shown to be noted by plasma It is in the diagram of functional relation to enter the concentration of nitrogen-atoms and penetrate into the depth of silicon oxide layer.Two can be generated by changing physical parameter A curve.First curve 11 is that the atom accelerated by higher is generated deeper into silica, on the contrary, curve 12 is more Change technological parameter to be generated compared with low-density.The superposition of two curves generates the master curve 13 for the characteristic that hopper is presented.Injection Relationship between the concentration of atom and/or molecule class is apparent.Region of the higher concentration instruction with higher defect sturcture, by There are the more spaces for accommodating subsequent starting material in this.In the technological parameter that plasma-activated period is controlled in a manner of specific aim Lasting change make it obtain introduce ion in depth with distribution as uniform as possible hopper.
As hopper, the hopper generated by plasma is substituted, it is contemplated that in a substrate at least one (at least the One substrate) on use TEOS (tetraethyl orthosilicate) oxide skin(coating).The usual density of this oxide is less than thermal oxide, thus basis Present invention compression is advantageous.Compression is occurred by heat treatment to set the porosity of the determination of the hopper.
An embodiment according to the present invention, is filled out by the way that the hopper to be applied to coating form on the first substrate It fills the hopper and occurs simultaneously especially advantageous with the hopper is formed, wherein the coating has included first starting material.
It is contemplated that hopper be with porosity be in porous layer in nanometer range or as with channel density Less than containing for 10nm, more preferably less than 5nm, even more preferably less than 2nm, more preferably less than 1nm, more preferably less than 0.5nm The layer in channel.
For the step of filling the hopper using the first starting material or the first starting material group, according to the present invention, it is contemplated that Following embodiments and combination thereof：
The hopper is exposed in ambiance,
Especially rinsed with deionized water,
With the fluid flushing formed containing starting material or by starting material, especially H2O、H2O2、NH4OH,
The hopper is exposed in any gas atmosphere, especially atomic gas, molecular gas, admixture of gas,
The hopper is exposed in the atmosphere containing vapor or hydrogen peroxide vapor, and
Deposition has been filled with superficial layer of the hopper as the first substrate of starting material.
Following compound can be starting material：O2、O3、N2、NH3、H2O、H2O2And/or NH4OH。
The more preferably scheme in addition to using water is regarded as using hydrogen peroxide vapor listed above.Hydrogen peroxide into One step, which is gathered around, has the advantage that its oxygen is higher to the ratio of hydrogen.In addition, hydrogen peroxide is higher than under specific temperature and/or via using High frequency field in MHz range can be dissociated into hydrogen and oxygen.
A Favourable implementations according to the present invention, the reinforcing of formation and the irreversible engagement of grown layers by by this One starting material diffuses in the conversion zone and occurs.
Another Favourable implementations according to the present invention, irreversible engagement be formed in usually less than 300 DEG C, it is advantageously small In 200 DEG C, more preferably less than 150 DEG C, even more preferably less than 100 DEG C, most preferably at a temperature of room temperature especially most 12 It, occur during more preferably up to 1 day, even more preferably at most 1 hour, most preferably up to 15 minutes.
Herein, if the irreversible engagement, which has, is more than 1.5 J/m2, especially greater than 2 J/m2, more preferably greater than 2.5 J/m2 Bond strength, then its is especially advantageous.
Bond strength can especially advantageously enhance, this is by during reaction, according to the present invention in the conversion zone The molal volume that being formed has is more than the product of the molal volume of the second starting material.Realize by this method on the second substrate at It is long, it is possible thereby to be closed the gap between the contact surface by chemical reaction according to the present invention.It is connect described in reducing as a result, Touch the distance between surface i.e. average distance and nullified space-minimized.
As long as the formation of hopper is occurred by plasma-activated by, especially between 10 and 600 kHz Activate frequency and/or between 0.075 and 0.2 watt/cm2Between power density and/or using between 0.1 and 0.6 millibar it Between pressure carry out pressure-loaded, it can be achieved that the additive effect such as contact surface smoothing and the contact surface it is hydrophilic Property significantly increases.
Alternatively, according to the present invention, the formation of hopper can be by using being especially compressed to a certain porosity in a controlled manner Tetraethoxy-silicane alkoxide layer as superficial layer occur.
Another Favourable implementations according to the present invention, provide superficial layer mainly by, especially substantially completely by especially It is unbodied by thermal oxidation generate silica form, and conversion zone by oxidizable material, especially mainly by, preferably Substantially completely it is made of Si, Ge, InP, GaP or GaN.The especially stable reaction for being particularly effectively closed existing gap is to pass through Oxidation is realized.
Herein, if the growth especially mainly formed by native silicon dioxide is arranged between the second contact surface and conversion zone Layer, then according to the present invention, its is especially advantageous.Grown layers are subjected to growth caused by reaction according to the present invention.Pass through amorphous Si O2 It is new formed and thus caused by the deformations of the grown layers especially swell, especially on the interface to the conversion zone and especially In gap area between the first and second contact surfaces, the growth is by Si-SiO2Transformation (7) takes place.Cause in this way The reduction of the distance between two contact surfaces or idle space reduce, and thus the bond strength between two substrates increases.Between Between 200 DEG C and 400 DEG C, preferably be generally between 200 DEG C and 150 DEG C, the temperature that is more preferably between 150 DEG C and 100 DEG C It spends, is most preferably especially advantageous between 100 DEG C of temperature between room temperature.
Herein, if grown layers have the average thickness A between 0.1nm and 5nm before the irreversible engagement of formation, Its is especially advantageous.Grown layers are thinner, then the reaction occurred by the grown layers between first and second starting material is faster and more holds Easily, especially the first starting material diffuses to the reaction of conversion zone by the grown layers.
An embodiment according to the present invention advantageously provides the formation for carrying out hopper in a vacuum.As a result, may be used It is polluted by unwanted material or compound to avoid hopper.
In another embodiment of the present invention, it advantageously provides in the step of filling of hopper is by being set forth below One or more carry out：
First contact surface is exposed in air to fill the reservoir using the oxygen contained in atmospheric humidity and/or air Slot,
By the first contact surface be exposed to especially mainly by, preferably almost by especially deionized H2O and/or H2O2 The fluid of composition,
First contact surface, which is exposed to, especially has the N of the ion energy within the scope of 0 to 200 eV2Gas and/or O2 Gas and/or Ar gas and/or especially by 95% Ar and 5% H2The formation gas of composition,
Vapor deposition with using it is any it is already indicated that starting material fill the hopper.
If hopper preferably between 0.1nm and 25nm, be more preferably between 0.1nm and 15nm, even more excellent Thickness R of the selected introductions between 0.1nm and 10nm, most preferably between 0.1nm and 5nm is formed, then is especially had to treatment progress Effect.In addition, embodiment according to the present invention, if just before forming the irreversible engagement between the hopper and the conversion zone Average distance B between 0.1nm and 15nm, especially between 0.5nm and 5nm, be more preferably between 0.5nm with It is advantageous between 3nm.
A kind of apparatus for carrying out the method is formed according to the present invention, have be used to form the hopper chamber and For filling the chamber of the hopper being especially separately provided and being used to form the chamber of pre- engagement being especially separately provided, own Chamber is all connected to each other directly via vacuum system.
In another embodiment, the filling of hopper can also be directly via air, i.e., in the chamber that can be opened to air In or simply without chuck but can it is semi-automatic and/or completely automatically processing chip structure on carry out.
From the description of following preferred exemplary embodiment and attached drawing is utilized, further advantage of the invention, feature and thin Section will become obvious.
Description of the drawings
Fig. 1 show immediately in make first substrate contacted with second substrate after as the method for the present invention first step,
Fig. 2 a and Fig. 2 b show be used to form more high bond strength as the method for the present invention other steps,
Fig. 3 is shown according to such as the other step of the method for the present invention, wherein substrate connect later the step of Fig. 1, Fig. 2 a and Fig. 2 b Tactile surface contacts with each other,
Fig. 4 show for formed between the substrates irreversible/permanent engagement as the present invention step,
Fig. 5 be shown according to fig. 3 with the step of Fig. 4 during the amplification of chemical/physical process that is carried out in two contact surfaces Figure,
The chemical/physical carried out on interface between two contact surfaces during Fig. 6 is shown according to fig. 3 and the step of Fig. 4 Another enlarged drawing of process, and
Fig. 7 shows the schematic diagram of hopper produced according to the invention.
Specific implementation mode
The identical reference numerals of identical or feature with phase same-action in figure.
The first contact surface 3 and the second of second substrate 2 of first substrate 1 is merely displayed in situation shown in Fig. 1 The section of processing chemical reaction is carried out during pre- engagement step between contact surface 4 or immediately after.The surface has pole Property OH bases terminal therefore be hydrophilic.First substrate 1 and second substrate 2 are by the OH bases and the H that are present on the surface2O molecules it Between and only H2The attraction of water bridge between O molecules is fixed.At least the hydrophily of first contact surface 3 is in previous steps Increased by the corona treatment of first contact surface 3.
Hopper 5 is formed according to the present invention by corona treatment in the superficial layer 6 being made of thermal silicon dioxide.It utilizes O of the ion energy within the scope of 0 and 2000 eV2Ion carries out the average thickness of hopper 5 caused by corona treatment R substantially 15nm, the ion form channel or hole in the superficial layer 6.
Similarly, H is used before step shown in Fig. 1 and after corona treatment2O is filled out as the first starting material Fill the hopper 5.The reduction type of ion present in corona treatment may be alternatively located in the hopper, especially O2、N2、 H2、Ar。
Therefore, contact surface 3,4 still has relatively wide spacing, particularly depends on existing between the contact surface 3,4 Water.Therefore, existing bond strength is relatively small and is generally between 100 mJ/cm2With 300 mJ/cm2Between, especially greater than 200 mJ/cm2.In this regard, it is previous it is plasma-activated play a decisive role, be particularly due to through plasma-activated The first contact surface 3 hydrophily increase and by the gas ions activate caused by smoothing effect.
Shown in Fig. 1 and be referred to as the method for pre- engagement preferably can in environment temperature or it is 50 DEG C maximum at carry out.Fig. 2 a and Fig. 2 b show hydrophilic engagement, and wherein Si-O-Si bridges are formed by-OH sealing end facial cleft solution water outlets.Method in Fig. 2 a and Fig. 2 b Continue substantially 300 hours at room temperature, substantially 60 hours at 50 DEG C.State in Fig. 2 b do not betide instruction at a temperature of and not Generate the hopper.
H is formed between contact surface 3,42O molecules and H is provided at least partly2O molecules are further to fill the reservoir Slot 5, as long as there is also free spaces.Other H2O molecules are removed.In the step of according to Fig. 1,3 to 5 are substantially existed Single OH bases or H2O layers and from according to the step of Fig. 1 to the step of a according to fig. 2 remove 1 to 3 single layer H2O is accommodated In the hopper 5.
In step shown in fig. 2 a, hydrogen bridge band is formed directly between siloxane group now, thus generates bigger Engaging force.So that contact surface 3,4 is more strongly attracted each other in this way and reduces the contact surface 3, the distance between 4. There is only 1 to 2 single OH bases between the contact surface 1,2 as a result,.
In step shown in figure 2b, successively according to the Reaction Separation H being hereafter inserted into2O molecules, in the contact table The covalent bond in silanol form is formed between face 3,4, is led to stronger engaging force and is required smaller space so that The contact surface 3, the distance between 4 further decreases, and meets directly with one another and last until being based on the contact surface 3,4 Reach minimum range shown in Fig. 3：
Si-OH+HO-Si↔Si-O-Si+H2O。
Until in the stage 3, be particularly due to the formation of the hopper 5, without exceedingly increasing temperature, even if on the contrary in room Also it may be allowed its progress under temperature.By this method, the processing step such as Fig. 1 to Fig. 3 quite can carefully be carried out.
In method and step shown in Fig. 4, temperature be preferably increased to maximum 500 DEG C, more preferably up to 300 DEG C, even More preferably up to 200 DEG C, 100 DEG C most preferably maximum, most preferably no more than room temperature, so as between the first and second contact surfaces Form irreversible or permanent engagement.Relatively low temperature is only possible compared with the prior art for these, because of the reservoir Slot 5 includes the first starting material for being reacted shown in Fig. 5 and Fig. 6：
Si+2H2O→SiO2+2H2。
At a temperature of aforementioned be slightly increased, H2O molecules diffuse to conversion zone 7 as the first starting material from hopper 5.This Diffusion can be in direct contact via the superficial layer 6 formed as oxide layer and grown layers 8 or exist via between the oxide layer Gap 9 and occur.Therefore, silica is the compound with the molal volume more than pure silicon, as the anti-of above-mentioned reaction Product 10 is answered to be formed by the conversion zone 7.The silica grows up on interface of the conversion zone 7 with grown layers 8 and thus makes to be formed For native oxide grown layers 8 layer along gap 9 Direction distortion.Herein, it is also desirable to the H from hopper2O molecules.
Due to there is the gap in nanometer range, so there is a possibility that the protuberance of native oxide layer 8, therefore can Reduce the stress in the contact surface 3,4.The contact surface 3, the distance between 4 reduces by this method, thus further It increases effective contact surface and thus further increases bond strength.It formed by this method, be closed all holes and in entire The unwelded product in part can fundamentally promote the enhancing of engaging force during what is formed on chip be welded to connect compared with the prior art. Bond types between two amorphous silicon faces being welded to one another are covalent and ionic portions mixed forms.
First starting material (H2O) with the previous reaction of the second starting material (Si) especially quickly or at alap temperature Occur in the conversion zone, as long as the average distance B between first contact surface 3 and the conversion zone 7 is as small as possible.
Therefore, the pretreatment of first substrate 1 and second substrate 2 are (by pasc reaction layer 7 and conduct grown layers 8 as thin as possible Natural oxide layer composition) selection be conclusive.According to native oxide layer provided by the present invention it is as thin as possible for Two reasons.The grown layers 8 are very thin so that it since (superficial layer is as oxide skin(coating) for the superficial layer 6 towards opposing substrate 1 Formed) it can be swelled in the reaction product 10 being newly formed in the conversion zone 7, and mainly in the region of nano gap 9.In addition, the phase Hope diffusion path as short as possible to obtain required effect soon and at alap temperature as far as possible.Similarly, first substrate 1 It is made of as the oxide skin(coating) of superficial layer 6 (hopper 5 is at least partially or fully formed in wherein) silicon layer and being formed thereon.
According to the present invention, correspondingly at least filling needs the first starting material for being closed the amount of nano gap 9 in hopper 5, It is received so that the grown layers 8 can occur most preferably to grow up in the shortest possible time or being closed this at alap temperature Rice gap 9.
Reference numerals list
1 first substrate
2 second substrates
3 first contact surfaces
4 second contact surfaces
5 hoppers
6 superficial layers
7 conversion zones
8 grown layers
9 nano gaps
10 reaction products
11 first curves
12 second curves
13 master curves
A average thickness
B average distances
R average thickness.

Claims (10)

1. the method that the first contact surface (3) of first substrate (1) is bonded to the second contact surface (4) of second substrate (2), This method has steps of：
First contact surface (3) superficial layer (6) in formed hopper (5), wherein pore size distribution with thickness increase and Reduction goes to zero,
The hopper (5) is at least partly filled with the first starting material or first group of starting material,
So that the first contact surface (3) is contacted with the second contact surface (4) and is connected with forming pre- engagement.
2. the method for claim 1 wherein the hopper (5) is formed by plasma-activated effect.
3. the method for claims 1 or 2 is store wherein being formed by tetraethoxy-silicane alkoxide layer is used as superficial layer (6) Liquid bath (5).
4. the method for claims 1 or 2, wherein the method further include below step：
Permanent engagement is formed between first and second contact surface (3,4), is filled in hopper (5) by making The first starting material react and made by the reaction described with the second starting material contained in the conversion zone (7) of second substrate (2) At least one of contact surface (3,4) deforms at least partly to strengthen the permanent engagement.
5. method as claimed in claim 4, wherein superficial layer (6) are made of unbodied material, and conversion zone (7) is by oxidable Material forms.
6. the method for claim 4, wherein there are grown layers, the grown layers between the second contact surface (4) and conversion zone (7) It is made of native silicon dioxide.
7. the method for claims 1 or 2, wherein the hopper (5) is to be formed under vacuum.
8. one or more of the step of method of claims 1 or 2, wherein the hopper (5) is by being set forth below, fills out It fills：
First contact surface (3) is exposed to comprising deionized H2O and/or H2O2Fluid, and
First contact surface (3) is exposed to N2Gas and/or O2Gas and/or Ar gas and/or include 95% Ar and 5% H2's Form gas.
9. the method for claims 1 or 2, the wherein hopper (5) are with the average thickness (R) between 0.1nm and 25nm It is formed.
10. the method for claim 4, wherein just being averaged between hopper (5) and conversion zone (7) before forming permanent engagement Distance (B) is between 0.1nm and 15nm.
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