SILICON-ON-INSULATOR WITH CRYSTALLINE SILICON OXIDE
20230005786 · 2023-01-05
Assignee
Inventors
- Pekka LAUKKANEN (Turku, FI)
- Mikhail Kuzmin (St. Petersburg, RU)
- Jaakko Mäkelä (Turku, FI)
- Marjukka Tuominen (Raisio, FI)
- Marko Punkkinen (Turku, FI)
- Antti Lahti (Turku, FI)
- Kalevi Kokko (Turku, FI)
- Juha-Pekka Lehtio (Turku, FI)
Cpc classification
H01L21/02271
ELECTRICITY
H01L23/3171
ELECTRICITY
H01L21/02172
ELECTRICITY
International classification
H01L21/762
ELECTRICITY
H01L21/02
ELECTRICITY
Abstract
A method for forming a semiconductor structure comprising a silicon-on-insulator layer structure with crystalline silicon oxide SiO.sub.x as the insulator material comprises: providing a crystalline silicon substrate having a substantially clean deposition surface in a vacuum chamber; heating the silicon substrate to an oxidation temperature To in the range of 550 to 1200 ° C.; supplying, while keeping the silicon substrate in the oxidation temperature, with an oxidation pressure P.sub.o in the range of 1.Math.10.sup.−8 to 1.Math.10.sup.−4 mbar in the vacuum chamber, molecular oxygen O.sub.2 into the vacuum chamber with an oxygen dose D.sub.o in the range of 0.1 to 1000 Langmuir; whereby a crystalline silicon oxide layer with a thickness of at least two molecular layers is formed within the silicon substrate, between a crystalline silicon base layer and a crystalline silicon top layer. Related semiconductor structures are described.
Claims
1. A semiconductor structure comprising a silicon-on-insulator layer structure with crystalline silicon oxide SiO.sub.x as the insulator material, comprising: a crystalline silicon base layer; a crystalline silicon oxide layer, with a thickness of at least two molecular layers, on the crystalline silicon base layer; and a crystalline silicon top layer on the crystalline silicon oxide layer.
2. A semiconductor structure as defined in claim 1, further comprising a cap layer on the crystalline silicon top layer.
3. A semiconductor structure as defined in claim 2, wherein the cap layer has a thickness of 1 to 500 nm.
4. A semiconductor structure as defined in claim 2, wherein the cap layer comprises silicon dioxide SiO.sub.2, aluminum oxide Al.sub.2O.sub.3, hafnium oxide HfO.sub.2, or titanium oxide TiO.sub.2 .
5. A semiconductor structure as defined in claim 1, wherein the crystal orientation is silicon {100}, silicon {111}, or silicon {110}.
6. A semiconductor structure as defined in claim 1, wherein the crystalline silicon base layer comprises a surface, wherein the surface is planar.
7. A semiconductor structure as defined in claim 1, wherein the crystalline silicon base layer comprises a three-dimensional structure.
8. A semiconductor structure as defined in claim 1, formed by: providing a crystalline silicon substrate have a substantially clean deposition surface in a vacuum chamber; heating the crystalline silicon substrate to an oxidation temperature T.sub.0 in a range of 550 to 1200° C.; supplying, while keeping the crystalline silicon substrate in the oxidation temperature, with an oxidation pressure P.sub.o in the range of 1.Math.10.sup.−8 to 1.Math.10.sup.−4 mbar in the vacuum chamber, molecular oxygen O.sub.2 into the vacuum chamber with an oxygen dose D.sub.o in the range of 0.1 to 1000 Langmuir; whereby at least part of the molecular oxygen supplied into the vacuum chamber is adsorbed onto the deposition surface and diffuses into the crystalline silicon substrate, and the crystalline silicon oxide layer is formed within the crystalline silicon substrate, between the crystalline silicon base layer and the crystalline silicon top layer.
9. A semiconductor structure as defined in claim 4, wherein the deposition surface is silicon {100}, silicon {111}, or silicon {110}.
10. A semiconductor structure as defined in claim 8, wherein the oxidation temperature T.sub.o is in a range of 550 to 850° C.
11. A semiconductor structure as defined in claim 8, wherein the oxidation temperature T.sub.o is in a range of 550 to 1000° C.
Description
DESCRIPTION OF THE DRAWINGS
[0010] The present description will be better understood from the following detailed description read in light of the accompanying drawings, wherein:
[0011]
[0012]
[0013]
[0014]
[0015]
[0016] The drawings of
DETAILED DESCRIPTION
[0017] The detailed description provided below in connection with the appended drawings is intended as a description of a number of embodiments and is not intended to represent the only forms in which the embodiments may be constructed, implemented, or utilized.
[0018] At least some of the embodiments and examples discussed below may provide, for example, a simple, substantially single-step process for forming a high-quality SOI structure with crystalline silicon oxide as the material of the insulator layer. Further, at least some of the embodiments and examples discussed below may provide, for example, a high-quality SOI layer structure suitable for being incorporated as part of various semiconductor devices. For example, the SOI layer structure may serve as a deposition surface for depositing semiconductor device layers on it.
[0019] The method 100 of
[0020] The method comprises providing, in operation 120, a crystalline silicon substrate 201 which has a substantially clean deposition surface 202 in a vacuum chamber.
[0021] The crystalline silicon substrate may be in the form of a plain silicon wafer of any appropriate diameter and thickness. Alternatively, the silicon substrate may be formed in any other appropriate configuration, shape, and size. For example, it may be cut from or etched on a silicon wafer. The silicon substrate may be a self-supporting structure or it may be a structure attached or formed on a carrier substrate or support structure. The silicon substrate may be a part of a larger structure or assembly incorporating also parts, structures, and elements not formed of silicon.
[0022] A deposition surface refers to a surface of the silicon substrate on which additional material may be introduced and/or adsorbed. With regard to the crystal orientation, the deposition surface may be, for example, a silicon {100}, silicon {111}, or silicon {110} surface.
[0023] Being substantially clean refers to the deposition surface being substantially free of any native silicon oxide or impurity atoms of any other type. “Substantially free” means that the concentration of foreign atoms and molecules on the silicon surface does not exceed 3.Math.10.sup.13 cm.sup.−2. Such substantially clean deposition surface may be provided as cleaned beforehand, i.e. before the method. Alternatively, a cleaning thereof may be included in the method, as illustrated by the optional cleaning operation 110 in the method of
[0024] The vacuum chamber may be any appropriate type of vacuum chamber of a system capable of producing a pressure of 1.Math.10.sup.−4 mbar or lower, preferably at least down to 1.Math.10.sup.−8 mbar, in the vacuum chamber. There may be any appropriate type of carrier or holder member on or to which the silicon substrate may be positioned or attached. Any appropriate type of heating and cooling system may be connected to such carrier or holder member to heat and cool the silicon substrate lying on it.
[0025] The method further comprises, in operation 130, heating the silicon substrate which has been provided in the vacuum chamber, to an oxidation temperature T.sub.o lying in the range of 550 to 1200° C., for example, in the range of 550 to 1000° C., 550 to 850° C., or 550 to 750° C.
[0026] In step 140, the method comprises supplying, while keeping the substrate in the oxidation temperature, molecular oxygen O.sub.2 into the vacuum chamber with an oxidation pressure P.sub.2 which lies in the range of 1.Math.10.sup.−8 to 1.Math.10.sup.−4 mbar, for example, in the range of 1.Math.10.sup.−7 to 1.Math.10.sup.−8 mbar. The oxygen supply is continued until an oxygen dose in the range of 0.1 to 1000 L, for example, in the range of 5 to 300 L has been supplied into the vacuum chamber.
[0027] Those ranges specified above define a parameter space within which the actual process parameters may be selected. Thus, the method may be carried out using different combinations of the actual process parameters, i.e. the oxidation temperature, the oxidation pressure, and the oxygen dose. For example, actual process parameters may be selected within any of the following parameter sub-spaces: To=550 to 700° C., Po=1.Math.10.sup.−7 to 1.Math.10.sup.−4 mbar, Do=10 to 50 L; To=650 to 700° C., Po=1.Math.10.sup.−7 to 1.Math.10.sup.−6 mbar, Do=50 to 100 L; To=650 to 750° C., Po=1.Math.10.sup.−7 to 5.Math.10.sup.−7 mbar, Do=50 to 300 L; To=700 to 750° C., Po=1.Math.10.sup.−5 to 5.Math.10.sup.−5 mbar, Do=5 to 50 L; To=550 to 600° C., Po=1.Math.10.sup.−7 to 5.Math.10.sup.−7 mbar, Do=5 to 75 L; and To =700 to 750° C., Po=5.Math.10.sup.−6 to 1.Math.10.sup.−5 mbar, Do=10 to 100 L.
[0028] The duration of the oxygen supply may vary depending, for example, on the oxygen pressure and the targeted oxygen dose. The oxygen pressure, in turn, may be affected, for example, by the detailed properties of the vacuum chamber and the oxygen supply arrangement. To ensure accurate control of the oxygen dose, the molecular oxygen may be supplied into the vacuum chamber for an oxidation period which is at least 0.5 seconds, for example, at least about 1 second, preferably at least 10 seconds. Increasing the length of the oxidation period may enable better control of the oxygen dose.
[0029] As a result of said oxygen supply with said oxidation pressure, oxidation time, and oxidation temperature of the silicon substrate, the oxygen supplied into the vacuum chamber is at least partially adsorbed onto the deposition surface and diffuses into the silicon substrate. Consequently, a crystalline silicon oxide layer with a thickness of at least two molecular layers is formed within the silicon substrate, between a crystalline silicon base layer and a crystalline silicon top layer. In other words, a SOI structure with crystalline silicon oxide SiO.sub.x layer as a dielectric layer is formed below a crystalline silicon top layer. Thereby, the method comprises forming a crystalline silicon oxide layer within an existing silicon crystal, without any need, for example, for additional deposition steps to form the crystalline silicon top layer. Then, the top layer may have basically or mostly the same diamond cubic crystal structure as the base layer. “Basically” and “mostly” refer to the fact that the crystalline silicon oxide layer may have a crystal structure deviating from the diamond cubic crystal structure, and that may have some effect on the crystal structure of the silicon top layer also, at least close to the Si/SiO.sub.x interface. On the other hand, the (2×1)+(1×2) reconstruction of the free surface of the crystalline silicon top layer affects the crystal structure of the top layer close to said free surface thereof.
[0030] According to established understanding in the art, when oxidizing crystalline silicon using known methods, the oxygen incorporation sites in the crystal lie at the deposition surface; see e.g. Miyamoto et al., Physical Review B 43, 9287, 1991.
[0031] However, the above method is based on a surprising observation that with suitably selected novel combination of the oxidation parameters, oxygen adsorbed onto the deposition surface may be made diffuse through a surface or top layer of the silicon substrate so that crystalline oxide is formed within the bulk silicon crystal clearly below the deposition surface. At the same time, silicon atoms from the bulk crystal of the silicon substrate may diffuse towards the outermost surface due to the incorporation of the oxygen atoms into the silicon substrate. Such diffused silicon atoms may form new structures on the deposition surface. The crystal structure of the crystalline oxide SiO.sub.x layer may be different from the diamond lattice of bulk silicon.
[0032] The semiconductor structure 200 of
[0033] The accurate thickness of the crystalline SiO.sub.x layer may vary and it may have a thickness of several nanometers. When formed by a method as discussed above with reference to
[0034] In the case of semiconductor structures manufactured using a method as discussed above with reference to
[0035] The method 300 of
[0036] Before the annealing, the semiconductor structure formed in the operations of 310 or 320 to 340 may be cooled to a temperature which substantially lower than the oxidation and post heating temperatures. Alternatively, the temperature of the silicon substrate/semiconductor structure may be adjusted directly from the oxidation temperature to the post heating temperature. In the case the oxidation temperature is equal to the post heating temperature, no adjustment is needed.
[0037] Feasibility of the methods discussed above was tested by oxidation procedure examples.
[0038] In first example, a 5 mm×10 mm rectangular Si sample was cut from an n-type Si (100) wafer to serve as a crystalline silicon substrate with a Si (100) deposition surface. The Si sample was attached via its shorter edges on a sample holder made of Mo and allowing direct current feeding through the Si sample. The sample holder was transferred into a manipulator located in a vacuum chamber of a multi-chamber vacuum system, and the Si sample was repeatedly rapidly heated up to a cleaning temperature of 1100 to 1200° C. to remove the native oxide and carbon contaminants from the Si (100) deposition surface. X-ray photoelectron spectroscopy (XPS) was used to confirm that the oxygen and carbon contaminants were effectively removed/desorbed from the deposition surface. Furthermore, low-energy electron diffraction (LEED) analysis showed a sharp (2×1)+(1×2) reconstruction arising from an inherent double-domain surface structure. Scanning-tunneling-microscopy (STM) images captured after the surface cleaning supported the presence of the double-domain reconstruction on large two-dimensional terraces.
[0039] After the cleaning phase, the Si sample with the clean Si (100) deposition surface was oxidized in the same vacuum system, using O.sub.2 gas introduced into the vacuum chamber via a leak valve. Before opening the leak valve, the temperature of the Si sample was increased to a heating temperature of 670° C. Then the O.sub.2 pressure in the vacuum chamber was increased to 1.Math.10.sup.−7 mbar (the pressure was measured by an ion gauge pressure meter), and the Si sample was oxidized at the heating temperature for 500 seconds, resulting in an oxidation dose of 50 Langmuir (L). Thereafter, the leak valve was closed and the Si heating was stopped simultaneously.
[0040] The STM images of
[0041] After completion of the oxidation of the Si sample, LEED image of the Si sample still showed a sharp (2×1)+(1×2) pattern, indicating that the outermost topmost surface layer of the sample was formed of crystalline silicon. On the other hand, O1s intensity measured from the sample by XPS clearly revealed the incorporation of oxygen atoms within the bulk silicon crystal, below the silicon top layer.
[0042] In second example, a Si sample was prepared and cleaned similarly to the first example discussed above. Oxidation was carried out basically similarly with the first example but with oxidation temperature of 600° C., using oxygen pressure of 1.Math.10.sup.−6 mbar and oxygen supply time of 75 s, resulting in oxygen dose of 75 L. Similarly to the first example, sharp (2×1)+(1×2) LEED pattern was observed and O1s intensity was measured by XPS, indicating formation of crystalline SOI structure also with those oxidation parameters.
[0043] In third example, basically similar to the first and the second examples, oxidation was carried out with oxidation temperature of 700° C., using oxygen pressure of 1.Math.10.sup.−4 mbar and oxygen supply time of 1 s, resulting in an oxygen dose of about 100 to 200 L. After the oxidation, LEED image of the sample showed only a weak (1×1), indicating presence of excess oxygen, not incorporated into the Si bulk crystal and forming crystalline SiO.sub.x, at the deposition surface. The sample was then annealed at a post-heating temperature of 700° C. for 10 minutes. The annealing resulted in sharp (2×1)+(1×2) LEED pattern, similar to that of
[0044] The method 500 of
[0045] Further, the method comprises, in operation 560, depositing a cap layer on the silicon top layer. The cap layer may comprise, for example, an oxide or nitride, and it may be amorphous or crystalline. The additional oxide layer may comprise, for example, silicon dioxide SiO.sub.2, aluminum oxide Al.sub.2O.sub.3, hafnium oxide HfO.sub.2, or titanium oxide TiO.sub.2. In other embodiments, it may comprise, for example, mixed composition of hafnium oxide and titanium oxide HfO.sub.2-TiO.sub.2, zirconium oxide ZrO.sub.2, cerium oxide CeO.sub.2, yttrium oxide Y.sub.2O.sub.3, zirconium silicate ZrSiO.sub.4, hafnium silicate HfSiO.sub.4, aluminum oxide Al.sub.2O.sub.3, hafnium silicon oxynitride HfSiON, hafnium silicon nitride, lanthanum oxide La.sub.2O.sub.3, bismuth silicon oxide Bi.sub.4Si.sub.2O.sub.12, tantalum oxide Ta.sub.2O.sub.5, tungsten oxide WO.sub.3, lanthanum aluminum oxide LaAlO.sub.3, barium strontium oxide Ba.sub.1-xSr.sub.xO.sub.3, lead (II) titanate PbTiO.sub.3, barium titanate BaTiO.sub.3, strontium titanate SrTiO.sub.3, or any appropriate mixture thereof. The cap layer may have a thickness, for example, in the range of 1 to 500, 1 to 400, or 3 to 300 nm.
[0046] The cap layer may be deposited, for example, by atomic layer deposition ALD or chemical vapor deposition CVD. Thus, the overall method 500 may be carried out using a method in accordance with any of those discussed above with reference to
[0047] The semiconductor structure 600 of
[0048] It has been found that for a semiconductor structure manufactured using a method in accordance with any of those discussed above with reference to
[0049] The effect of such band bending on the band structure in a semiconductor structure as that of
[0050] The presence of the assumed effect schematically illustrated in
[0051] In the examples discussed above with reference to
[0052] Semiconductor structures manufactured as described above with reference to
[0053] A semiconductor structure as that illustrated in
[0054] In fourth example, two 5 mm×10 mm rectangular pieces were diced from an n-type Si (100) wafer to serve as a Si sample substrate and a Si reference substrate. The substrates were then cleaned in vacuum inside a vacuum chamber of a multi-chamber vacuum system by repeatedly rapidly heating them up to a cleaning temperature of 1100° C.
[0055] Following this cleaning procedure, the Si sample substrate was subjected to a heating temperature of 650° C., and an outer surface of the sample substrate was oxidized at an O.sub.2 pressure of 1.Math.10.sup.−7 mbar, resulting in an oxidation dose of 50 L, in order to produce a SOI layer structure according to the invention, after which HfO.sub.2 films with thicknesses of 25 nm were grown by ALD, using water and tetrakis(dimethylamido)hafnium(IV) (TDMAH) as the precursors, on the oxidized sample substrate and the reference substrate.
[0056] After the deposition of HfO.sub.2, circular gate-metal pads with diameters of 100 microns were deposited by sputtering 10 nm of chromium followed by 50 nm of gold through a shadow mask onto the HfO.sub.2 films in order to fabricate two metal-oxide-semiconductor (MOS) structures: a MOS capacitor sample and a MOS capacitor reference, comprising either the sample substrate or the reference substrate as the semiconductor, respectively. The MOS capacitor structures were then taken out of the vacuum system and connected to an LCR meter, using conductive silver paste to form back contacts.
[0057]
[0058] In fifth example, a MOS capacitor sample and a MOS capacitor reference were prepared and connected to an LCR meter similarly to the fourth example discussed above. However, in contrast to the fourth example, the step of cleaning sample and reference substrates in vacuum was replaced by a standard RCA cleaning procedure. The sample and reference substrates were also subjected to additional post-metallization annealing at a temperature of 400° C. prior to the addition of silver paste to form the back contacts.
[0059]
[0060] Although the subject matter has been described in language specific to structural features and/or methodological acts, it is to be understood that the subject matter defined in the appended claims is not necessarily limited to the specific features or acts described above. Rather, the specific features and acts described above are disclosed as example forms of implementing the claims.
[0061] It will be understood that the benefits and advantages described above may relate to one embodiment or may relate to several embodiments. The embodiments are not limited to those that solve any or all of the stated problems or those that have any or all of the stated benefits and advantages. It will further be understood that reference to ‘an’ item refers to one or more of those items.
[0062] The term “comprising” is used in this specification to mean including the feature(s) or act(s) followed thereafter, without excluding the presence of one or more additional features or acts.
[0063] It is to be noted that the embodiments of the claims are not limited to those discussed above, but further embodiments may exist within the scope of the claims.