Multi-function equipment implementing fabrication of high-k dielectric layer
11322348 · 2022-05-03
Assignee
Inventors
Cpc classification
H01L21/02192
ELECTRICITY
H01L29/517
ELECTRICITY
C23C16/45542
CHEMISTRY; METALLURGY
H01L21/28194
ELECTRICITY
H01J37/32568
ELECTRICITY
H01L21/28185
ELECTRICITY
H01L29/513
ELECTRICITY
C23C16/45538
CHEMISTRY; METALLURGY
International classification
H01L21/02
ELECTRICITY
C23C16/455
CHEMISTRY; METALLURGY
Abstract
A multi-function equipment implements a method of fabricating a thin film. The multi-function equipment according to the invention includes a reaction chamber, a plasma source, a plasma source power generating unit, a bias electrode, an AC (Alternating Current) voltage generating unit, a DC (Direct current) bias generating unit, a metal chuck, a first precursor supply source, a second precursor supply source, a carrier gas supply source, an oxygen supply source, a nitrogen supply source, an inert gas supply source, an automatic pressure controller, and a vacuum pump.
Claims
1. A multi-function equipment for fabricating a thin film, said multi-function equipment comprising: a reaction chamber; a plasma source, disposed in the reaction chamber and at a top of the reaction chamber; a plasma source power generating unit, being electrically connected to the plasma source, and being controlled to output an AC power to the plasma source; a bias electrode, disposed in the reaction chamber and at a bottom of the reaction chamber; an AC voltage generating unit, being electrically connected to the bias electrode, and being controlled to selectively output an AC voltage or the AC voltage combined with a DC bias to the bias electrode to control an energy of bombardment by a non-reactive gas plasma; a DC bias generating unit, being electrically connected to the bias electrode, and being controlled to selectively output a positive DC bias or a negative DC bias to the bias electrode to control the energy of bombardment by the non-reactive gas plasma; a metal chuck, disposed on the bias electrode, for holding a semi-product of the device; a first precursor supply source, connected with the reaction chamber via a first control valve, and being controlled to supply a first precursor of a thin film to the reaction chamber; a second precursor supply source, connected with the reaction chamber via a second control valve, and being controlled to supply a second precursor of the thin film to the reaction chamber; a carrier gas supply source, connected with the reaction chamber via a first flow controller, and being controlled to supply a carrier gas to the reaction chamber; an oxygen supply source, connected with the top of the reaction chamber via a second flow controller, and being controlled to supply an oxygen-containing gas, the oxygen-containing gas being ionized by the AC power of the plasma source into an oxygen plasma; a nitrogen supply source, connected with the top of the reaction chamber via a second flow controller, and being controlled to supply a nitrogen-containing gas, the nitrogen-containing gas being ionized by the AC power of the plasma source into a nitrogen plasma; an inert gas supply source, connected with the top of the reaction chamber via a third flow controller, and being controlled to supply an inert gas, the inert gas being ionized by the AC power of the plasma source into a non-reactive gas plasma; an automatic pressure controller; and a vacuum pump, connected with the bottom of the reaction chamber via the automatic pressure controller, and automatically controlling a pumping rate via the automatic pressure controller to achieve an ideal process pressure; wherein said multi-function equipment is used to fabricate the thin film by performing the steps of: performing an ALD process to form M atomic-layer-deposited films of the thin film in sequence on the semi-product of the device, wherein M is an integer larger than 1; and for N assigned films among the M atomic-layer-deposited films, bombarding the N assigned films by the non-reactive gas plasma during or after cycles of the ALD process to finish the said thin film, and to result in an annealing effect such that a defect density of the N assigned films is reduced, wherein N is a natural number and less than or equal to M.
2. The multi-function equipment of claim 1, wherein the metal chuck has an adjustable tilt angle relative to the bias electrode.
Description
BRIEF DESCRIPTION OF THE APPENDED DRAWINGS
(1)
(2)
(3)
(4)
(5)
(6)
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DETAILED DESCRIPTION OF THE INVENTION
(9) Please refer to
(10) As shown in
(11) In one embodiment, the semiconductor layer can be formed of Si, Ge, SiGe, GeSn, silicon on insulator, germanium on insulator, group III-V compound, group II-VI compound, and group IV-VI compound. The metal layer can be formed of platinum, rhodium, titanium, tungsten, copper, aluminum, Al—Si—Cu alloy, Al—Cu alloy, titanium nitride, tantalum nitride, heavily doped polysilicon and so on.
(12) Also as shown in
(13) The ALD process adopted by the invention has the following advantages: (1) having the capability to control the formation of the material in nano-metric scale; (2) having the capability to control the film thickness more precisely; (3) having the capability of large-area production; (4) having excellent uniformity; (5) having excellent conformality; (6) having pinhole-free structure; (7) having low defect density; and (8) low deposition temperature, etc. The ALD process adopted by the invention can form the atomic-layer-deposited films 10.
(14) In one embodiment, the oxide can be HfO.sub.2, ZrO.sub.2, Al.sub.2O.sub.3, La.sub.2O.sub.3, SiO.sub.2, TiO.sub.2, Y.sub.2O.sub.3, etc.
(15) In particular, during fabrication of the M atomic-layer-deposited films 10, N assigned films 12 among the M atomic-layer-deposited films 10 are bombarded by a non-reactive gas plasma during or after cycles of the ALD process to result in an annealing effect such that a defect density of the N assigned films 12 is reduced, where N is a natural number and less than or equal to M. In
(16) In the example shown in
(17) In the example shown in
(18) In the example shown in
(19) In one embodiment, an inert gas used to generate the non-reactive gas plasmas can be Ar, He, Ne, He/Ar, He/N.sub.2, He/Ne, etc.
(20) Generally, in the plasma process, Ar is widely used as a working gas for a plasma source. On the other hand, He is generally used as a buffer gas in a vapor deposition process, which serves as a non-flammable gas to control the working pressure. Compared with the Ar plasma, the He plasma has a higher energy because He has a smaller radius such that He has a higher ionization energy. In addition, since the mass of He is small, the damage caused by He plasma is lower than that caused by Ar plasma. Therefore, the assigned film 12 is bombarded with a non-reactive gas plasma such as He plasma, and the energy is transferred to the surface of the assigned film 12 by plasma bombardment, thereby the energy causes an annealing effect. The increase in the surface temperature of the assigned film 12 enhances the migration of the adatoms adsorbed to the surface of the assigned film 12, which facilitates the improvement of the film quality of the assigned film 12 and reduces the defect density of the assigned film 12. Another effect caused by an increase in temperature of the assigned film 12 facilitates the removal of ligands of precursors adsorbed to the surface of the assigned film 12.
(21) Thereby, the high-k dielectric layer 1 according to the invention has a leakage current density less than 1×10.sup.4 A/cm.sup.2 when a capacitance equivalent thickness (CET) of the high-k dielectric layer 1 according to the invention is less than 2 nm. Moreover, the high-k dielectric layer 1 of the invention is applied to a semiconductor device and has a thickness ranging from 1 nm to 50 nm, and therefore, the high-k dielectric layer 1 of the invention can replace the conventional ultra-thin SiO.sub.2 film.
(22) A method of fabricating a high-k dielectric layer 1, as shown in
(23) During fabrication of the M atomic-layer-deposited films 10, the method according to invention is, for N assigned films 12 among the M atomic-layer-deposited films 10, to bombard the N assigned films 12 by a non-reactive gas plasma during or after cycles of the ALD process to finish the high-k dielectric layer 1, and to result in an annealing effect such that a defect density of the N assigned films 12 is reduced, where N is a natural number and less than or equal to M. The arrangement relationship between the atomic-layer-deposited films 11 without bombardment by a non-reactive gas plasma and the assigned films 12 with bombardment by the non-reactive gas plasma of the high-k dielectric layer 1 according to the invention has been described in detail above, and will not be described in detail herein.
(24) The material used to form the semiconductor layer and the inert gas used to generate the non-reactive gas plasma have been described in detail above, and will not be described herein.
(25) In one embodiment, the oxide is HfO.sub.2. The precursor of supplying Hf element can be HfCl.sub.4, HfI.sub.4, HfCl.sub.2[N(SiMe.sub.3).sub.2].sub.2, HfCp.sub.2Me.sub.2, HfCp.sub.2Cl.sub.2, Hf(CpMe).sub.2Me.sub.2, Hf(CpMe).sub.2(OMe)Me, Hf(CpMe).sub.2(OiPr)Me, Hf(CpMe).sub.2(mmp)Me, Hf(Cp)(NMe.sub.2).sub.3, Hf(CpMe)(NMe.sub.2).sub.3, Hf(Cp.sub.2CMe.sub.2)Me.sub.2, Hf(Cp.sub.2CMe.sub.2)Me(OMe), Hf(OiPr).sub.4, Hf(OtBu).sub.4, Hf(OtBu).sub.2(mmp).sub.2, Hf(OtBu)(NEtMe).sub.3, Hf(mmp).sub.4, Hf(mp).sub.4, Hf(ONEt.sub.2).sub.4, Hf(NMe.sub.2).sub.4, Hf(NEt.sub.2).sub.4, Hf(NEtMe).sub.4, Hf[N(SiMe.sub.3).sub.2].sub.2Cl.sub.2, Hf(NO.sub.3).sub.4, etc. The precursor of supplying O element can be O.sub.2 plasma, N.sub.2O plasma, O.sub.3, H.sub.2O, H.sub.2O.sub.2, etc.
(26) In another embodiment, the oxide is ZrO.sub.2. The precursor of supplying Zr element can be ZrCl.sub.4, ZrI.sub.4, ZrCp.sub.2Cl.sub.2, ZrCp.sub.2Me.sub.2, ZrCp.sub.2Me(OMe), ZrCp(NMe.sub.2).sub.3, Zr(CpMe).sub.2Me.sub.2, Zr(CpMe).sub.2Me(OMe), Zr(CpMe)(NMe.sub.2).sub.3, Zr(CpEt)(NMe.sub.2).sub.3, Zr(Cp.sub.2CMe.sub.2)Me.sub.2, Zr(Cp.sub.2CMe.sub.2)Me(OMe), Zr(OiPr).sub.4, Zr(OiPr).sub.2(dmae).sub.2, Zr(OtBu).sub.4, Zr(OtBu).sub.2(dmae).sub.2, Zr(dmae).sub.4, Zr(thd).sub.4, Zr(NMe.sub.2).sub.4, Zr(NEt.sub.2).sub.4, Zr(NEtMe).sub.4, Zr[N(SiMe.sub.3).sub.2].sub.2Cl.sub.2, Zr(MeAMD).sub.4, etc. The precursor of supplying O element can be O.sub.2 plasma, N.sub.2O plasma, O.sub.3, H.sub.2O, H.sub.2O.sub.2, etc.
(27) In another embodiment, the oxide is Al.sub.2O.sub.3. The precursor of supplying Al element can be AlCl.sub.3, AlBr.sub.3, AlMe.sub.3, AlMe.sub.2Cl, AlMe.sub.2OiPr, AlEt.sub.3, Al(OEt).sub.3, Al(OnPr).sub.3, Al(mmp).sub.3, Al(NEt.sub.2).sub.3, Al(NiPr.sub.2).sub.3, Al(iPrAMD)Et.sub.2, etc. The precursor of supplying O element can be O.sub.2 plasma, N.sub.2O plasma, O.sub.3, H.sub.2O, H.sub.2O.sub.2, etc.
(28) In another embodiment, the oxide is TiO.sub.2. The precursor of supplying Ti element can be TiF.sub.4, TiCl.sub.4, TiI.sub.4, Ti(CpMe.sub.5)(OMe).sub.3, Ti(CpMe)(OiPr).sub.3, Ti(OMe).sub.4, Ti(OEt).sub.4, Ti(OiPr).sub.4, Ti(OiPr).sub.2(dmae).sub.2, Ti(OiPr).sub.2(thd).sub.2, Ti(trhd).sub.2(O(CMe.sub.2Et).sub.2, Ti(OBu).sub.4, Ti(NMe.sub.2).sub.4, TiCp.sub.2((iPrN).sub.2C(NHiPr)), etc. The precursor of supplying O element can be O.sub.2 plasma, N.sub.2O plasma, O.sub.3, H.sub.2O, H.sub.2O.sub.2, etc.
(29) In another embodiment, the oxide is La.sub.2O.sub.3. The precursor of supplying La element can be La(thd).sub.3, La[N(SiMe.sub.3).sub.2].sub.3, La(iPrAMD).sub.3, La(iPrfAMD).sub.3, La(Cp).sub.3, La(CpEt).sub.3, La(CpiPr).sub.3, etc. The precursor of supplying O element can be O.sub.2 plasma, N.sub.2O plasma, O.sub.3, H.sub.2O, H.sub.2O.sub.2, etc.
(30) In another embodiment, the oxide is SiO.sub.2. The precursor of supplying Si element can be SiCl.sub.4, Si.sub.2Cl.sub.6, SiCl.sub.3H, SiCl.sub.2H.sub.2, SiH.sub.4, Si(OMe).sub.4, Si(OEt).sub.4, Si(OEt).sub.3((CH.sub.2).sub.3NH.sub.2), Si(OtPe).sub.3OH, HMDS, SiH.sub.2(N(CH.sub.3).sub.2).sub.2, SiH.sub.2(NHtBu).sub.2, SiH.sub.2(NEt.sub.2).sub.2, SiH(N(CH.sub.3).sub.2).sub.3, Si(NCO).sub.4, MeOSi(NCO).sub.3, etc. The precursor of supplying O element can be O.sub.2 plasma, N.sub.2O plasma, O.sub.3, H.sub.2O, H.sub.2O.sub.2, etc.
(31) In another embodiment, the oxide is Y.sub.2O.sub.3. The precursor of supplying Y element can be Y(thd).sub.3, YCp.sub.3, Y(CpMe).sub.3, Y(CpEt).sub.3, Y(iPrAMD).sub.3, etc. The precursor of supplying O element can be O.sub.2 plasma, N.sub.2O plasma, O.sub.3, H.sub.2O, H.sub.2O.sub.2, etc.
(32) In one embodiment, the non-reactive gas plasmas has a flow rate ranging from 1 sccm to 1000 sccm.
(33) In one embodiment, the non-reactive gas plasmas has a working pressure ranging from 100 torr to 10.sup.−3 torr.
(34) Please refer to
(35) As shown in
(36) The plasma source 31 is disposed in the reaction chamber 30 and at a top 302 of the reaction chamber 30. The plasma source power generating unit 32 is electrically connected to the plasma source 31, and is controlled to output an AC power to the plasma source 31. The bias electrode 33 is disposed in the reaction chamber 30 and at a bottom 304 of the reaction chamber 30. The AC voltage generating unit 34 is electrically connected to the bias electrode 33, and is controlled to selectively output an AC voltage or the AC voltage combined with a DC bias to the bias electrode 33 to control an energy of bombardment by a non-reactive gas plasma. In one embodiment, the AC voltage generating unit 34 is controlled to selectively output an AC voltage or the AC voltage combined with a DC bias.
(37) The DC bias generating unit 35 is electrically connected to the bias electrode 33, and is controlled to selectively output a positive DC bias or a negative DC bias to the bias electrode 33 to control the energy of bombardment by the non-reactive gas plasma. In one embodiment, the DC bias generating unit 35 is controlled to selectively output a positive DC bias or a negative DC bias.
(38) The metal chuck 36 is disposed on the bias electrode 33, and holds a semi-product of the semiconductor device 2.
(39) The first precursor supply source 37 is connected with the reaction chamber 30 via a first control valve 372, and is controlled to supply a first precursor of an oxide to the reaction chamber 30. The second precursor supply source 38 is connected with the reaction chamber 30 via a second control valve 382, and is controlled to supply a second precursor of the oxide to the reaction chamber 30.
(40) The carrier gas supply source 44 is connected with the reaction chamber 30 via a first flow controller 442, and is controlled to supply a carrier gas to the reaction chamber 30.
(41) The oxygen supply source 39 is connected with the top 302 of the reaction chamber 30 via a second flow controller 392, and is controlled to supply an oxygen gas, the oxygen gas being ionized by the AC power of the plasma source 31 into an oxygen plasma. The inert gas supply source 40 is connected with the top 302 of the reaction chamber 30 via a third flow controller 402, and is controlled to supply an inert gas, the inert gas being ionized by the AC power of the plasma source 31 into a non-reactive gas plasma. The vacuum pump 42 is connected with the bottom 304 of the reaction chamber 30 via the automatic pressure controller 41, and automatically controls a pumping rate via the automatic pressure controller 41 to achieve an ideal process pressure.
(42) It is emphasized that the multi-function equipment 3 according to the invention can perform non-reactive gas plasma bombardment in situ, that is, the multi-function equipment 3 according to the invention can perform a non-reactive gas plasma bombardment in the reaction chamber 30 without the need of moving the semi-product of the semiconductor device 2 to another chamber. Further, during fabrication of the M atomic-layer-deposited films 10, the multi-function equipment 3 according to the invention can perform a non-reactive gas plasma bombardment for N assigned films 12 among the M atomic-layer-deposited films 10 during or after cycles of the ALD process.
(43) Also as shown in
(44) The invention proves that the high-k dielectric layer of the invention has a low leakage current density. The invention prepares a specimen labeled as “DHe”. The specimen DHe consists of a plurality of atomic-layer-deposited films of HfO.sub.2 on a p-type silicon substrate having a resistivity of 1-10 Ω-cm, and the lower half of the atomic-layer-deposited films is bombarded by He plasma. The invention also prepares a specimen labeled as “THe”. The specimen THe consists of a plurality of atomic-layer-deposited films of HfO.sub.2 on a p-type silicon substrate having a resistivity of 1-10 Ω-cm, and the upper half of the atomic-layer-deposited films is bombarded by He plasma. In contrast, the invention also prepares a specimen labeled as “Hf0”. The specimen Hf0 consists of a plurality of atomic-layer-deposited films of HfO.sub.2 on a p-type silicon substrate having a resistivity of 1-10 Ω-cm, and all of the atomic-layer-deposited films are not bombarded by He plasma. Referring to
(45) Next, the specimen DHe, the specimen THe and the specimen Hf0 are respectively coated with Pt and Al on the atomic-layer-deposited films of HfO.sub.2 and the backside of silicon substrate thereof as gate electrodes and lower electrodes to form metal-oxide-semiconductor structures. Thereafter, the specimen DHe, the specimen THe, and the specimen Hf0 are treated with a post-metallization annealing (PMA) at 400° C. for 30 minutes in an atmosphere of a forming gas of 5% H.sub.2 and 95% N.sub.2.
(46) Please refer to
(47) Please refer to Table 1, the capacitance equivalent thicknesses (CET), effective dielectric constants (K.sub.eff), gate leakage current densities (J.sub.g) and interfacial state defect densities (D.sub.it) of the PMA-treated specimen DHe, the PMA-treated specimen THe, and the PMA-treated specimen Hf0 are listed in Table 1. The gate leakage current density (J.sub.g) of the specimen is defined as the flat-band voltage applied to the gate electrode subtracts 1 V. CETs of the PMA-treated specimen DHe, the PMA-treated specimen THe, and the PMA-treated specimen Hf0 are less than 2 nm.
(48) TABLE-US-00001 TABLE 1 with PMA treatment Hf0 DHe THe CET(nm) 1.61 1.85 1.61 K.sub.eff 9.69 8.43 9.7 J.sub.g(A/cm.sup.2) 1.67 × 10.sup.−4 1.34 × 10.sup.−5 2.44 × 10.sup.−5 D.sub.it(cm.sup.−2eV.sup.−1) 7.25 × 10.sup.11 3.46 × 10.sup.11 4.60 × 10.sup.11
(49) The results listed in Table 1 confirm that both the leakage current densities of the PMA-treated specimen DHe and the PMA-treated specimen THe are lower than 1×10.sup.−4 A/cm.sup.2, which are better than that of the PMA-treated specimen Hf0 not bombarded by He plasma. It is evident that the He plasma bombardment can effectively improve the film quality of the high-k dielectric layer of the invention and reduce the defect density of the high-k dielectric layer of the invention.
(50) Please refer to
(51) With the example and explanations above, the features and spirits of the invention will be hopefully well described. Those skilled in the art will readily observe that numerous modifications and alterations of the device may be made while retaining the teaching of the invention. Accordingly, the above disclosure should be construed as limited only by the metes and bounds of the appended claims.