Method of controlling solid phase diffusion of boron dopants to form ultra-shallow doping regions
09899224 ยท 2018-02-20
Assignee
Inventors
- Steven P. Consiglio (Albany, NY, US)
- Robert D. Clark (Livermore, CA, US)
- David L. O'Meara (Albany, NY, US)
Cpc classification
H01L21/2254
ELECTRICITY
International classification
Abstract
A method is provided for forming an ultra-shallow boron doping region in a semiconductor device. The method includes depositing a diffusion filter layer on a substrate, the diffusion filter containing a boron nitride layer, a boron oxynitride layer, a silicon nitride layer, or a silicon oxynitride layer, and depositing a boron dopant layer on the diffusion filter layer, the boron dopant layer containing boron oxide, boron oxynitride, or a combination thereof, with the proviso that the diffusion filter layer and the boron dopant layer do not contain the same material. The method further includes heat-treating the substrate to form the ultra-shallow boron dopant region in the substrate by controlled diffusion of boron from the boron dopant layer through the diffusion filter layer and into the substrate.
Claims
1. A method of forming an ultra-shallow boron doping region in a semiconductor device, the method comprising: depositing a diffusion filter layer on a substrate, the diffusion filter layer containing a boron nitride layer, a boron oxynitride layer, a silicon nitride layer, or a silicon oxynitride layer; depositing a boron dopant layer on the diffusion filter layer, the boron dopant layer containing boron oxide, boron oxynitride, or a combination thereof, with the proviso that the diffusion filter layer and the boron dopant layer do not contain the same material; and heat-treating the substrate to form the ultra-shallow boron dopant region in the substrate by controlled diffusion of boron from the boron dopant layer through the diffusion filter layer and into the substrate, wherein the diffusion filter layer, the boron dopant layer, or both the diffusion filter layer and the boron dopant layer, are deposited by atomic layer deposition (ALD) using alternating gaseous exposures of a boron amide precursor and a reactant gas.
2. The method of claim 1, further comprising prior to the heat-treating, depositing a cap layer on the boron dopant layer.
3. The method of claim 2, wherein the cap layer contains a boron nitride layer.
4. The method of claim 1, further comprising removing the diffusion filter layer and the boron dopant layer from the substrate.
5. The method of claim 1, wherein the heat-treating is performed in an inert atmosphere.
6. The method of claim 1, wherein the substrate contains a raised feature or a recessed feature, and the diffusion filter layer and the boron dopant layer are conformally deposited on the raised feature or in the recessed feature.
7. The method of claim 1, wherein the boron dopant layer contains boron oxide and the reactant gas includes H.sub.2O, O.sub.2, or O.sub.3, or a combination of two or more thereof.
8. The method of claim 1, wherein the boron dopant layer contains boron oxynitride and the reactant gas includes a) H.sub.2O, O.sub.2, or O.sub.3, and NH.sub.3, or b) NO, NO.sub.2, or N.sub.2O, and optionally one or more of H.sub.2O, O.sub.2, O.sub.3, and NH.sub.3.
9. The method of claim 1, wherein the diffusion filter layer is deposited using alternating gaseous exposures of the boron amide precursor and the reactant gas containing NH.sub.3.
10. The method of claim 1, wherein the diffusion filter layer and the boron dopant layer are deposited in the same process chamber, and wherein the substrate is maintained at the same substrate temperature during deposition of the diffusion filter layer and the boron dopant layer.
11. A method of forming an ultra-shallow boron doping region in a semiconductor device, the method comprising: depositing a diffusion filter layer on a substrate, the diffusion filter layer containing a boron nitride layer, a boron oxynitride layer, a silicon nitride layer, or a silicon oxynitride layer; depositing a boron dopant layer on the diffusion filter layer, the boron dopant layer containing boron oxide, boron oxynitride, or a combination thereof, with the proviso that the diffusion filter layer and the boron dopant layer do not contain the same material; and heat-treating the substrate to form the ultra-shallow boron dopant region in the substrate by controlled diffusion of boron from the boron dopant layer through the diffusion filter layer and into the substrate, wherein the diffusion filter layer, the boron dopant layer, or both the diffusion filter layer and the boron dopant layer, are deposited by atomic layer deposition (ALD) using alternating gaseous exposures of an organoboron precursor and a reactant gas.
12. The method of claim 11, wherein the boron dopant layer contains boron oxide and the reactant gas includes H.sub.2O, O.sub.2, or O.sub.3, or a combination of two or more thereof.
13. The method of claim 11, wherein the boron dopant layer contains boron oxynitride and the reactant gas includes a) H.sub.2O, O.sub.2, or O.sub.3, and NH.sub.3, or b) NO, NO.sub.2, or N.sub.2O, and optionally one or more of H.sub.2O, O.sub.2, O.sub.3, and NH.sub.3.
14. The method of claim 11, wherein the diffusion filter layer is deposited using alternating gaseous exposures of the organoboron precursor and the reactant gas containing NH.sub.3.
15. The method of claim 11, further comprising prior to the heat-treating, depositing a cap layer on the boron dopant layer.
16. The method of claim 11, further comprising removing the diffusion filter layer and the boron dopant layer from the substrate.
17. The method of claim 11, wherein the heat-treating is performed in an inert atmosphere.
18. The method of claim 11, wherein the substrate contains a raised feature or a recessed feature, and the diffusion filter layer and the boron dopant layer are conformally deposited on the raised feature or in the recessed feature.
19. A method of forming an ultra-shallow boron doping region in a semiconductor device, the method comprising: depositing a diffusion filter layer on a substrate, the diffusion filter layer containing a boron nitride layer; depositing a boron dopant layer on the diffusion filter layer, the boron dopant layer containing boron oxide or boron oxynitride; depositing a cap layer on the boron dopant layer; heat-treating the substrate in an inert atmosphere to form the ultra-shallow boron dopant region in the substrate by controlled diffusion of boron from the boron dopant layer through the diffusion filter layer and into the substrate; and removing the diffusion filter layer and the boron dopant layer from the substrate.
20. The method of claim 15, wherein the cap layer contains a boron nitride layer.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) In the accompanying drawings:
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DETAILED DESCRIPTION OF SEVERAL EMBODIMENTS
(12) Methods for forming ultra-shallow boron dopant regions in semiconductor devices by solid phase diffusion from a boron dopant layer through a diffusion filter layer into a substrate layer are disclosed in various embodiments. The boron dopant regions can include, for example, ultra-shallow source-drain extensions for planar transistors, FinFETs, or tri-gate FETs. Other applications of ultra-shallow boron dopant region formation can include channel doping in replacement gate process flows, and for FinFET, or extremely thin silicon on insulator (ET-SOI) devices. Devices with extremely thin alternative semiconductor channels may also be doped using the disclosed method, for instance germanium on insulator devices (GeOI) or Ge FinFETs, and III-V channel devices such as GaAs, InGaAs, or InGaSb FinFETs. In addition, devices formed in amorphous Si or polycrystalline Si layers, such as EDRAM devices may utilize the disclosed method to adjust the Si doping level.
(13) One skilled in the relevant art will recognize that the various embodiments may be practiced without one or more of the specific details, or with other replacement and/or additional methods, materials, or components. In other instances, well-known structures, materials, or operations are not shown or described in detail to avoid obscuring aspects of various embodiments of the invention. Similarly, for purposes of explanation, specific numbers, materials, and configurations are set forth in order to provide a thorough understanding of the invention. Furthermore, it is understood that the various embodiments shown in the drawings are illustrative representations and are not necessarily drawn to scale.
(14) Reference throughout this specification to one embodiment or an embodiment means that a particular feature, structure, material, or characteristic described in connection with the embodiment is included in at least one embodiment of the invention, but do not denote that they are present in every embodiment. Thus, the appearances of the phrase in one embodiment in various places throughout this specification are not necessarily referring to the same embodiment of the invention.
(15) Previous work on boron doping by solid state diffusion includes the use of a B.sub.2O.sub.3 dopant layer as a source of boron dopants, where the B.sub.2O.sub.3 dopant layer is in direct contact with the substrate and boron atoms diffuse directly into the substrate from the B.sub.2O.sub.3 dopant layer during a heat-treating. The thickness, boron content, and boron depth profile of the resulting boron dopant region in the substrate is a function of the thickness of the B.sub.2O.sub.3 dopant layer and the heat-treating conditions, including substrate temperature and duration of the heat-treating. However, new methods are needed to better control the properties of the boron dopant region.
(16) Embodiments of the invention provide a novel new approach to control the properties of the boron-doped region, including the junction depth. According to one embodiment, an inert and thermally stable diffusion filter layer containing boron nitride (BN) is positioned between the substrate and the boron dopant layer. According to other embodiments, the diffusion filter layer can contain a boron oxynitride layer, a silicon nitride layer, or a silicon oxynitride layer. The diffusion filter layer can act as a blocking layer to impede boron diffusion and control the properties of the boron doping region, including the thickness, boron content, and boron depth profile. In one example, the diffusion filter layer may be used to achieve less than boron saturation concentration in the boron doping region. For example, a thickness of the diffusion filter layer can be used to control the properties of the boron doping region. In one example, the diffusion filter layer can include a BN layer deposited by atomic layer deposition (ALD) and a B.sub.2O.sub.3 dopant layer can also be deposited by ALD. The use of ALD provides a method of manufacturing a boron-doped semiconductor device with excellent control over the thickness of the BN layer, the boron dopant layer, and the properties of the boron doping region.
(17) According to one embodiment, a method is provided for forming an ultra-shallow boron doping region in a semiconductor device. The method includes depositing a diffusion filter layer on a substrate, the diffusion filter layer containing a boron nitride layer, a boron oxynitride layer, a silicon nitride layer, or a silicon oxynitride layer, and depositing a boron dopant layer on the diffusion filter layer, where the boron dopant layer contains boron oxide, boron oxynitride, or a combination thereof, with the proviso that the diffusion filter layer and the boron dopant layer do not contain the same material. The method further includes heat-treating the substrate to form the ultra-shallow boron dopant region in the substrate by controlled diffusion of boron from the boron dopant layer through the diffusion filter layer and into the substrate.
(18) A significant drawback to using a pure B.sub.2O.sub.3 dopant layer is the extreme air instability of B.sub.2O.sub.3. This is due to its high reactivity with moisture in the ambient which results in boric acid formation that has a high vapor pressure. The inventors have realized that a cap layer may be formed on the B.sub.2O.sub.3 dopant layer to protect the B.sub.2O.sub.3 dopant layer from the moisture. According to one embodiment, the cap layer can contain or consist of BN. The use of the cap layer allows for heat-treating a substrate containing the B.sub.2O.sub.3 dopant layer in non-clustered thermal processing system.
(19) According to one embodiment, the boron dopant layer can contain boron oxynitride (BNO). In some examples, a composition of the boron oxynitride can range from nitrogen-doped boron oxide with B and O as the major elements to an oxygen-doped boron nitride with B and N as the major elements. Increasing the nitrogen-content and reducing the oxygen-content in the BNO allows for further controlling the properties of the boron doping region since the presence of nitrogen increases the thermal stability of BNO relative to B.sub.2O.sub.3. In one embodiment, a cap layer may be formed on the BNO layer to protect the BNO layer from moisture.
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(21) The diffusion filter layer 102 and the boron dopant layer 104 may be deposited by atomic layer deposition (ALD). In one example, a B.sub.2O.sub.3 dopant layer 104 may be deposited by ALD by a) providing a substrate in a process chamber configured for performing an ALD process, b) exposing the substrate to a vapor phase boron amide or an organoborane precursor, c) purging/evacuating the process chamber, d) exposing the substrate to a reactant gas containing H.sub.2O, O.sub.2, or O.sub.3, a combination thereof, e) purging/evacuating the process chamber, and f) repeating steps b)-e) any number of times until the B.sub.2O.sub.3 dopant layer has a desired thickness. In another example, a BNO dopant layer 104 or a BNO diffusion filter layer 102 may be deposited by ALD using in step d) a reactant gas containing 1) H.sub.2O, O.sub.2, or O.sub.3, and NH.sub.3, or 2) NO, NO.sub.2, or N.sub.2O, and optionally one or more of H.sub.2O, O.sub.2, O.sub.3, and NH.sub.3. In one example, a BN diffusion filter layer 102 may be deposited by ALD using a reactant gas containing NH.sub.3 in step d).
(22) According to embodiments of the invention, the boron amide may be include a boron compound of the form L.sub.nB(NR.sup.1R.sup.2).sub.3 where L is a neutral Lewis base, n is 0 or 1, and each of R.sup.1 and R.sup.2 may be selected from alkyls, aryls, fluoroalkyls, fluoroaryls, alkoxyalkyls, and aminoalkyls. Examples of boron amides include B(NMe.sub.2).sub.3, (Me.sub.3)B(NMe.sub.2).sub.3, and B[N(CF.sub.3).sub.2].sub.3. According to embodiments of the invention, the organoborane may include a boron compound of the form L.sub.nBR.sup.1R.sup.2R.sup.3 where L is a neutral Lewis base, n is 0 or 1, and each of R.sup.1, R.sup.2 and R.sup.3 may be selected from alkyls, aryls, fluoroalkyls, fluoroaryls, alkoxyalkyls, and aminoalkyls. Examples of boron amides include BMe.sub.3, (Me.sub.3N)BMe.sub.3, B(CF.sub.3).sub.3, and (Me.sub.3N)B(C.sub.6F.sub.3).
(23) According to some embodiments, a diffusion filter layer 102 containing a silicon nitride layer or a silicon oxynitride layer may be deposited or grown on the substrate 100 using methods well known to those skilled in the art.
(24) In some examples, a thickness of each of the diffusion filter layer 102 and the boron dopant layer 104 can be 10 nanometers (nm), or less, or 4 nm or less, for example between 1 nm and 4 nm, between 2 nm and 4 nm, or between 3 nm and 4 nm. However, other thicknesses may be used.
(25) The film structure in
(26) In some examples, a thickness of the ultra-shallow boron dopant region 106 can be between 1 nm and 10 nm or between 2 nm and 5 nm. However, those skilled in the art will readily realize that the lower boundary of the ultra-shallow boron dopant region 106 in the substrate 100 may not be abrupt but rather characterized by gradual decrease in dopant concentration.
(27) Following the heat-treating and formation of the ultra-shallow boron dopant region 106, the boron dopant layer 104 and the diffusion filter layer 102 may be removed using a dry etching process or a wet etching process. The resulting structure is depicted in
(28) According to another embodiment, as depicted in
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(30) The film structure in
(31) Following the heat-treating and formation of the ultra-shallow boron dopant region 116, the patterned boron dopant layer 114 and the patterned diffusion filter layer 112 may be removed using a dry etching process or a wet etching process. The resulting structure is depicted in
(32) According to another embodiment, as depicted in
(33) According to another embodiment, the patterned cap layer 115 in
(34) According to another embodiment, the patterned diffusion filter layer 112 in
(35) According to one embodiment of the invention, two or more of diffusion filter layer, the boron dopant layer, and the cap layer may be deposited in a single process chamber. This prevents exposure of these layers to ambient moisture and other oxidizing gases in air. In one example, ALD of these layers may be achieved during sequential processing in the process chamber where a boron nitride layer is deposited using alternating gaseous exposures of a boron amide or an organoboron precursor and a first reactant gas (e.g., NH.sub.3), thereafter a boron oxide layer is deposited using alternating gaseous exposures of a boron amide or an organoboron precursor and a second reactant gas (e.g., H.sub.2O, O.sub.2, or O.sub.3, or a combination of two or more thereof), and thereafter a boron nitride cap layer is deposited using alternating gaseous exposures of a boron amide or an organoboron precursor and a third reactant gas (e.g., NH.sub.3 for a boron nitride layer). In one example, the boron oxide layer may be replaced by a boron oxynitride layer that is deposited using alternating gaseous exposures of a boron amide or an organoboron precursor and a fourth reactant gas (e.g., a) H.sub.2O, O.sub.2, or O.sub.3, and NH.sub.3, or b) NO, NO.sub.2, or N.sub.2O, and optionally one or more of H.sub.2O, O.sub.2, O.sub.3, and NH.sub.3. According to one embodiment, the diffusion filter layer and the boron dopant layer may be deposited in the same process chamber, where the substrate is maintained at the same substrate temperature during deposition of the diffusion filter layer and the boron dopant layer
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(38) The SIMS depth profiles in
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(42) A plurality of embodiments for forming ultra-shallow boron dopant region in a substrate by solid phase diffusion of boron from a boron dopant layer through a diffusion filter layer into the substrate have been disclosed in various embodiments. The foregoing description of the embodiments of the invention has been presented for the purposes of illustration and description. It is not intended to be exhaustive or to limit the invention to the precise forms disclosed. This description and the claims following include terms that are used for descriptive purposes only and are not to be construed as limiting. Persons skilled in the relevant art can appreciate that many modifications and variations are possible in light of the above teaching. Persons skilled in the art will recognize various equivalent combinations and substitutions for various components shown in the Figures. It is therefore intended that the scope of the invention be limited not by this detailed description, but rather by the claims appended hereto.