METHOD FOR PERMANENTLY BONDING WAFERS

Abstract

This invention relates to a method for bonding of a first contact surface of a first substrate to a second contact surface of a second substrate with the following steps, especially the following sequence: forming a first reservoir in a surface layer on the first contact surface and a second reservoir in a surface layer on the second contact surface, the surface layers of the first and second contact surfaces being comprised of respective native oxide materials of one or more second educts respectively contained in reaction layers of the first and second substrates, partially filling the first and second reservoirs with one or more first educts; and reacting the first educts filled in the first reservoir with the second educts contained in the reaction layer of the second substrate to at least partially strengthen a permanent bond formed between the first and second contact surfaces.

Claims

1. A method for bonding of a first contact surface of a first substrate to a second contact surface of a second substrate comprising the following steps: forming a first reservoir in a surface layer on the first contact surface and a second reservoir in a surface layer on the second contact surface, the surface layers of the first and second contact surfaces being comprised of respective native oxide materials of one or more second educts respectively contained in reaction layers of the first and second substrates, the second educts being selected from the group consisting of Ge, Al, GaP, GaAs, InP, InSb, InAs, GaSb, GaN, InN, Al.sub.xGa.sub.1−xAs, In.sub.xGa.sub.1−xN, InAlP, CuInSe.sub.2, CuInGaSe.sub.2, CuInGaS.sub.2, and In.sub.2−xSn.sub.2−xO.sub.3−y; partially filling the first and second reservoirs with one or more first educts; and reacting the first educts filled in the first reservoir with the second educts contained in the reaction layer of the second substrate to at least partially strengthen a permanent bond formed between the first and second contact surfaces.

2. The method as claimed in claim 1, wherein the reacting takes place by diffusion of the first educts of the first reservoir into the reaction layer of the second substrate.

3. The method as claimed in claim 1, wherein the reacting takes place at a temperature between room temperature and 200° C., during a maximum 12 day period.

4. The method as claimed in claim 1, wherein the permanent bond has a bond strength of greater than 1.5 J/m.sup.2.

5. The method as claimed in claim 1, wherein a reaction product is formed in the reaction layer of the second substrate during the reacting, said reaction product having a greater molar volume than a molar volume of the second educts contained in the reaction layer of the second substrate.

6. The method as claimed in claim 1, wherein the reservoirs are formed by plasma activation.

7. The method as claimed in claim 1, wherein the surface layer of said first contact surface is comprised of an amorphous material produced by thermal oxidation.

8. The method as claimed in claim 1, wherein a growth layer is between the second contact surface and the reaction layer of the second substrate, said growth layer being comprised of the native oxide material of the second educts contained in the reaction layer of the second substrate.

9. The method as claimed in claim 8, wherein before the reacting, the growth layer and/or the surface layer has an average thickness “A” between 1 angstrom and 10 nm.

10. The method as claimed in claim 1, wherein one of said first reservoir and said second reservoir is formed in a vacuum.

11. The method as claimed in claim 1, wherein the reservoirs are filled by one or more of the following steps: exposing the first contact surface to an atmosphere, exposing the first contact surface to at least one fluid selected from the group consisting of deionized H.sub.2O and H.sub.2O.sub.2, and exposing the first contact surface to at least one gas selected from the group consisting of N.sub.2, O.sub.2, and Ar with an ion energy in the range from 0 to 2000 eV.

12. The method as claimed in claim 1, wherein the permanent bond is additionally strengthened by a reaction of the first educts filled in the second reservoir with the second educts contained in the reaction layer of the first substrate.

13. The method as claimed in claim 1, wherein an average distance (B) between the first reservoir and the reaction layer of the second substrate immediately before the reacting is between 0.1 nm and 15 nm.

14. The method as claimed in claim 1, wherein the first reservoir and the second reservoir are dimensioned to hold the first educts, wherein portions of the first educts held by the first and second reservoirs respectively react with the reaction layers of the second and first substrates, and wherein remaining portions of the first educts held by the first and second reservoirs do not respectively react with the reaction layers of the second and first substrates and remain within the first and second reservoirs to hinder a formation of bubbles therein.

15. The method as claimed in claim 1, wherein the second educts are selected from the group consisting of Ge and Al.

16. A method of bonding a first contact surface of a first substrate to a second contact surface of a second substrate comprising the following steps: forming a first reservoir in a surface layer on the first contact surface and a second reservoir in a surface layer on the second contact surface, the surface layers of the first and second contact surfaces being comprised of respective native oxide materials of one or more second educts respectively contained in reaction layers of the first and second substrates, the second educts being selected from the group consisting of Ge, Al, GaP, GaAs, InP, InSb, InAs, GaSb, GaN, InN, Al.sub.xGa.sub.1−xAs, In.sub.xGa.sub.1−xN, InAlP, CuInSe.sub.2, CuInGaSe.sub.2, CuInGaS.sub.2, and In.sub.2−xSn.sub.xO.sub.3−y; partially filling the first and second reservoirs with one or more first educts; forming a prebond connection between the first and second contact surfaces by bringing one or more portions of the first contact surface into contact with one or more portions of the second contact surface such that gaps are formed between the first and second contact surfaces at areas located between the respective contacted portions of the first and second contact surfaces; and reacting the first educts filled in the first reservoir with the second educts contained in the reaction layer of the second substrate to form a reaction product to at least partially strengthen a permanent bond formed between the first and second contact surfaces, the reaction product being formed between the reaction layer of the second substrate and the surface layer of the second substrate, the reaction serving to bulge the surface layer of the second substrate toward the first contact surface to close the gaps and at least partially strengthen the permanent bond, the reaction serving to deform a portion of the reaction layer of the second substrate into the reaction product.

17. The method as claimed in claim 16, wherein the permanent bond has a bond strength which is at least twice a strength of the prebond connection.

18. The method as claimed in claim 16, wherein the areas in which the gaps are formed are filled with the bulged surface layer.

19. The method as claimed in claim 16, wherein the permanent bond is additionally strengthened by a reaction of the first educts filled in the second reservoir with the second educts contained in the reaction layer of the first substrate.

20. The method as claimed in claim 16, wherein the second educts are selected from the group consisting of Ge and Al.

21. A method of bonding a first substrate to a second substrate, the first and second substrates being respectively comprised of first and second reaction layers, the method comprising the following steps: producing first and second surface layers respectively on the first and second reaction layers by reacting the first and second reaction layers with a first educt, the first and second surface layers having molar volumes that are respectively greater than molar volumes of the first and second reaction layers, the first and second surface layers respectively comprising first and second contact surfaces; the first and second reaction layers being comprised of one or more second educts; forming first and second reservoirs respectively in the first and second surface layers; filling the first and second reservoirs with the first educt; and bringing a plurality of portions of the first contact surface into contact with a plurality of portions of the second contact surface to cause the first educt from the first and second reservoirs to respectively diffuse through the second and first surface layers and react with the second and first reaction layers, thereby bringing all of the portions of the first contact surface into contact with all of the portions of the second contact surface and permanently bonding the first substrate to the second substrate.

22. The method as claimed in claim 20, wherein the second educts are selected from the group consisting of Ge, Al, GaP, GaAs, InP, InSb, InAs, GaSb, GaN, InN, Al.sub.xGa.sub.1−xAs, In.sub.xGa.sub.1−xN, InAlP, CuInSe.sub.2, CuInGaSe.sub.2, CuInGaS.sub.2, and In.sub.2−xSn.sub.xO.sub.3−y.

23. The method as claimed in claim 22, wherein the second educts are selected from the group consisting of Ge and Al.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0108] FIG. 1a shows a first step of the method as claimed in the invention immediately after the first substrate makes contact with the second substrate,

[0109] FIG. 1b shows an alternative first step of the method as claimed in the invention immediately after the first substrate makes contact with the second substrate,

[0110] FIGS. 2a and 2b show other steps of the method as claimed in the invention for forming a higher bond strength,

[0111] FIG. 3 shows another step of the method as claimed in the invention which follows the steps according to FIG. 1, FIG. 2a and FIG. 2b, with substrate contact surfaces which are in contact,

[0112] FIG. 4 shows a step as claimed in the invention for formation of an irreversible/permanent bond between the substrates,

[0113] FIG. 5 shows an enlargement of the chemical/physical processes which proceed on the two contact surfaces during the steps according to FIG. 3 and FIG. 4,

[0114] FIG. 6 shows a further enlargement of the chemical/physical processes which proceed on the interface between the two contact surfaces during the steps according to FIG. 3 and FIG. 4 and

[0115] FIG. 7 shows a diagram of the production of the reservoir as claimed in the invention.

[0116] The same or equivalent features are identified with the same reference numbers in the figures.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

[0117] In the situation which is shown in FIG. 1a only one extract of the chemical reactions which proceed during or immediately after the prebond step between a first contact surface 3 of a first substrate 1 and a second contact surface 4 of a second substrate 2 is shown. Surface layers 6, 6′ adjoin the contact surfaces 3, 4 respectively and are formed from oxidizable, native silicon dioxide and are very thin. The surfaces are terminated with polar OH groups and are accordingly hydrophilic. The first substrate 1 and the second substrate 2 are held by the force of attraction of the hydrogen bridges between the OH groups present on the surface and the H.sub.2O molecules and also between the H.sub.2O molecules alone. The hydrophilicity of at least the first contact surface 3 is increased by plasma treatment of the first contact surface 3 in a preceding step.

[0118] It is especially advantageous to additionally subject the second contact surface 4 to plasma treatment, especially at the same time with the plasma treatment of the first contact surface 3 according to the alternative embodiment.

[0119] A reservoir 5 in the surface layer 6 consisting of native silicon dioxide, as well as in the alternative embodiment according to FIG. 1b a second opposing reservoir 5′ in the surface layer 6′, are formed as claimed in the invention by plasma treatment. Plasma treatment with O.sub.2 ions with ion energies in the range between 0 and 2000 eV yields an average thickness R of the reservoir 5 of roughly 10 nm, the ions forming channels or pores in the surface layer 6 (and optionally the surface layer 6′).

[0120] Between the reservoir formation layer 6 and the reaction layer 7 there is a growth layer 8 on the second substrate 2 which can be at the same time at least partially the reservoir formation layer 6′. Accordingly there can additionally be another growth layer between the reservoir formation layer 6′ and the reaction layer 7′.

[0121] Likewise the reservoir 5 (and optionally the reservoir 5′) is filled at least largely with H.sub.2O as the first educt prior to the step shown in FIG. 1 and after plasma treatment. Reduced species of the ions present in the plasma process can also be located in the reservoir, especially O.sub.2, N.sub.2, H.sub.2, Ar.

[0122] The contact surfaces 3, 4 still have a relatively wide gap, especially dictated by the water present between the contact surfaces 3, 4, after making contact in the stage shown in FIGS. 1a and 1b. Accordingly the existing bond strength is relatively low and is roughly between 100 mJ/cm.sup.2 and 300 mJ/cm.sup.2, especially more than 200 mJ/cm.sup.2. In this connection the prior plasma activation plays a decisive part, especially due to the increased hydrophilicity of the plasma-activated first contact surface 3 and a smoothing effect which is caused by the plasma activation.

[0123] The process which is shown in FIG. 1 and which is called prebond can preferably proceed at ambient temperature or a maximum 50° C. FIGS. 2a and 2b show a hydrophilic bond, the Si—O—Si bridge arising with splitting of water by —OH terminated surfaces. The processes in FIGS. 2a and 2b last roughly 300 h at room temperature. At 50° C. roughly 60 h. The state in FIG. 2b occurs at the indicated temperatures without producing the reservoir 5 (or reservoirs 5, 5′).

[0124] Between the contact surfaces 3, 4, H.sub.2O molecules are formed and provide at least partially for further filling in the reservoir 5 to the extent there is still free space. The other H.sub.2O molecules are removed. In the step according to FIG. 1 roughly 3 to 5 individual layers of OH groups or H.sub.2O are present and 1 to 3 monolayers of H.sub.2O are removed or accommodated in the reservoir 5 from the step according to FIG. 1 to the step according to FIG. 2a.

[0125] In the step shown in FIG. 2a the hydrogen bridge bonds are now formed directly between siloxane groups, as a result of which a greater bond force arises. This draws the contact surfaces 3, 4 more strongly to one another and reduces the distance between the contact surfaces 3, 4. Accordingly there are only 1 to 2 individual layers of OH groups between the contact surfaces 1, 2.

[0126] In the step shown in FIG. 2b, in turn with separation of H.sub.2O molecules according to the reaction which has been inserted below, covalent compounds in the form of silanol groups are now formed between the contact surfaces 3, 4 which lead to a much stronger bond force and require less space so that the distance between the contact surfaces 3, 4 is further reduced until finally the minimum distance shown in FIG. 3 is reached based on the contact surfaces 3, 4 directly meeting one another:

Si—OH+HO—Si←Si—O—Si+H.sub.2O

[0127] Up to stage 3, especially due to the formation of the reservoir 5 (and optionally of the additional reservoir 5′), it is not necessary to unduly increase the temperature, rather to allow it to proceed even at room temperature. In this way an especially careful progression of the process steps according to FIG. 1 to FIG. 3 is possible.

[0128] In the process step shown in FIG. 4, the temperature is preferably increased to a maximum 500° C., more preferably to a maximum 300° C., even more preferably to a maximum 200° C., most preferably to a maximum 100° C., most preferably of all not above room temperature in order to form an irreversible or permanent bond between the first and the second contact surface. These temperatures which are relatively low, in contrast to the prior art, are only possible because the reservoir 5 (and optionally in addition the reservoir 5′) encompasses the first educt for the reaction shown in FIGS. 5 and 6:

Si+2H.sub.2O.fwdarw.SiO.sub.2+2H.sub.2

[0129] Between the second contact surface 4 and the reaction layer 7 there is a growth layer 8 which can be identical to the surface layer 6′. To the extent a reservoir 5′ has been formed according to the second embodiment, between the first contact surface 3 and another reaction layer 7′ which corresponds to the reaction layer 7 there is also another growth layer 8′, the reactions proceeding essentially reciprocally. By increasing the molar volume and diffusion of the H.sub.2O molecules, especially on the interface between the surface layer 6′ and the reaction layer 7 (and optionally in addition on the interface between the surface layer 6 and the reaction layer 7′), volume in the form of a growth layer 8 increases, due to the objective of minimizing the free Gibb's enthalpy enhanced growth taking place in regions in which gaps 9 are present between the contact surfaces 3, 4. The gaps 9 are closed by the increase in the volume of the growth layer 8. More exactly:

[0130] At the aforementioned slightly increased temperatures, H.sub.2O molecules diffuse as the first educt from the reservoir 5 to the reaction layer 7 (and optionally from the reservoir 5′ to the reaction layer 7′). This diffusion can take place either via a direct contact of the surface layer 6 and growth layer 8 which are formed as native oxide layers (or via a gap 9 or from a gap 9 which is present between the oxide layers). There, silicon dioxide, therefore a chemical compound with a greater molar volume than pure silicon, is formed as a reaction product 10 of the aforementioned reaction from the reaction layer 7. The silicon dioxide grows on the interface of the reaction layer 7 with the growth layer 8 (or the interface of the reaction layer 7′ with the growth layer 8′) and thus deforms the layer of the growth layer 8 formed as native oxide in the direction of the gaps 9. Here H.sub.2O molecules from the reservoir are also required.

[0131] Due to the existence of the gaps which are in the nanometer range, there is the possibility of bulging of the native oxide layer (growth layer 8 and optionally growth layer 8′), as a result of which stresses on the contact surfaces 3, 4 can be reduced. In this way the distance between the contact surfaces 3, 4 is reduced, as a result of which the active contact surface and thus the bond strength are further increased. The weld connection which has arisen in this way, which closes all pores, and which forms over the entire wafer, in contrast to the products in the prior art which are partially not welded, fundamentally contributes to increasing the bond force. The type of bond between the two native silicon oxide surfaces which are welded to one another is a mixed form of covalent and ionic portion.

[0132] The aforementioned reaction of the first educt (H.sub.2O) with the second educt (Si) takes place in the reaction layer 7 especially quickly or at temperatures as low as possible to the extent an average distance B between the first contact surface 3 and the reaction layer 7 is as small as possible.

[0133] Therefore the choice of the first substrate 1 and the selection/pretreatment of the second substrate 2 which consists of a reaction layer 7 (and optionally 7′) of silicon and a native oxide layer as thin as possible as a growth layer 8 (and optionally 8′) are decisive. A native oxide layer as thin as possible is provided as claimed in the invention for two reasons. The growth layer 8 is very thin, especially due to additional thinning, so that it can bulge through the newly formed reaction product 10 on the reaction layer 7 toward the surface layer 6 of the opposite substrate 1, which surface layer is likewise made as a native oxide layer, predominantly in regions of the nanogaps 9. Furthermore, diffusion paths as short as possible are desired in order to achieve the desired effect as quickly as possible and at a temperature as low as possible. The first substrate 1 likewise consists of a silicon layer and a native oxide layer as thin as possible present on it as a surface layer 6 in which the reservoir 5 is formed at least partially or completely.

[0134] The reservoir 5 (and optionally the reservoir 5′) as claimed in the invention is filled at least accordingly with the amount of the first educt which is necessary to close the nanogaps 9 so that an optimum growth of the growth layer 8 (and optionally 8′) can take place to close the nanogaps 9 in a time as short as possible and/or at a temperature as low as possible.

REFERENCE NUMBER LIST

[0135] 1 first substrate [0136] 2 second substrate [0137] 3 first contact surface [0138] 4 second contact surface [0139] 5, 5′ reservoir [0140] 6, 6′ surface layer [0141] 7, 7′ reaction layer [0142] 8, 8′ growth layer [0143] 9 nanogaps [0144] 10 reaction product [0145] 11 first profile [0146] 12 second profile [0147] 13 sum curve [0148] A average thickness [0149] B average distance [0150] R average thickness