US20070010037A1 - Superlattice nanocrystal si-sio2 electroluminescence device - Google Patents
Superlattice nanocrystal si-sio2 electroluminescence device Download PDFInfo
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- US20070010037A1 US20070010037A1 US11/175,797 US17579705A US2007010037A1 US 20070010037 A1 US20070010037 A1 US 20070010037A1 US 17579705 A US17579705 A US 17579705A US 2007010037 A1 US2007010037 A1 US 2007010037A1
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- 238000005401 electroluminescence Methods 0.000 title claims abstract description 58
- 239000002159 nanocrystal Substances 0.000 title claims abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 147
- 229910021420 polycrystalline silicon Inorganic materials 0.000 claims abstract description 117
- 229920005591 polysilicon Polymers 0.000 claims abstract description 117
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 73
- 238000000034 method Methods 0.000 claims abstract description 63
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 62
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 62
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 62
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 62
- 239000000758 substrate Substances 0.000 claims abstract description 38
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 36
- 238000000151 deposition Methods 0.000 claims abstract description 35
- 238000000137 annealing Methods 0.000 claims abstract description 18
- 230000008021 deposition Effects 0.000 claims abstract description 16
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 15
- 229910021417 amorphous silicon Inorganic materials 0.000 claims abstract description 14
- 238000004544 sputter deposition Methods 0.000 claims abstract description 14
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 26
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 18
- 150000002910 rare earth metals Chemical class 0.000 claims description 18
- 239000010703 silicon Substances 0.000 claims description 18
- 229910007667 ZnOx Inorganic materials 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 229910052691 Erbium Inorganic materials 0.000 claims description 5
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 5
- 229910052771 Terbium Inorganic materials 0.000 claims description 5
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052779 Neodymium Inorganic materials 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- 229910000077 silane Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 239000013077 target material Substances 0.000 claims description 2
- 229910008062 Si-SiO2 Inorganic materials 0.000 abstract description 21
- 229910006403 Si—SiO2 Inorganic materials 0.000 abstract description 21
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 230000003647 oxidation Effects 0.000 description 23
- 238000007254 oxidation reaction Methods 0.000 description 23
- 229910052814 silicon oxide Inorganic materials 0.000 description 7
- 239000010408 film Substances 0.000 description 6
- 238000002513 implantation Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 3
- 239000012212 insulator Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- -1 rare earth ions Chemical class 0.000 description 2
- 150000003376 silicon Chemical class 0.000 description 2
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 description 1
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000002784 hot electron Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 229910021423 nanocrystalline silicon Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
- H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
- H10H20/80—Constructional details
- H10H20/81—Bodies
- H10H20/822—Materials of the light-emitting regions
- H10H20/826—Materials of the light-emitting regions comprising only Group IV materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
- H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
- H10H20/80—Constructional details
- H10H20/81—Bodies
Definitions
- This invention generally relates to integrated circuit (IC) fabrication and, more particularly, to a nanocrystalline superlattice silicon (Si)-silicon dioxide SiO 2 electroluminescence (EL) device and light-emitting diode (LED) device.
- IC integrated circuit
- Si nanocrystalline superlattice silicon
- EL electroluminescence
- LED light-emitting diode
- Green emission color was observed from the sample post-annealed at 600° C., and blue for the sample post-annealed at a temperature of 900° C. From I-V measurements, Sato gave the light emission threshold voltages: 4.0V for red emission, 9.0V for green and 9.5V for blue emission. This data suggests very promising Si quantum dots EL and LED applications.
- the external quantum efficiency depends on the rare earth ions incorporated, and ranges from 10% (for a Tb doped MOS) to 0.1% (for an Yb doped MOS).
- Much more stable light emitting MOS devices have been fabricated using Er-doped SRO (Si-rich silicon oxide) films as the gate dielectric, but the external quantum efficiency is reduced to 0.2%. With respect to the light emission mechanism, it is thought that Er pumping occurs partly due to the impact of hot electrons, and partly by energy transfer from the Si nanostructures to the rare earth ions, depending on the Si excess in the film.
- Dr. Pasquarello has proposed a theory for the photoemission associated with a Si—SiO2 interface.
- Si 2p core-level shifts occur at the Si(001)-SiO2, and depend linearly on nearest-neighbor oxygen atoms. Second nearest-neighbor effects turn out to be negligibly small. Therefore, an efficient photoemission spectra requires that all Si oxidation states be present at the interface. Based on this theory, the making of a high density Si—SiO2 interface is a critical issue for EL device applications.
- the present invention describes processes for the fabrication of a superlattice nanocrystalline Si and SiO2 structures for EL and LED device applications. Technologies are presented for making a multi-layer Si—SiO2 superlattice structure using CVD polysilicon deposition, thermal oxidation, and rare earth element implantation processes.
- a method for forming a superlattice nanocrystal Si—SiO 2 EL device comprises: providing a Si substrate; forming an initial SiO 2 layer overlying the Si substrate; forming an initial polysilicon layer overlying the initial SiO 2 layer; forming SiO 2 layer overlying the initial polysilicon layer; repeating the polysilicon and SiO 2 layer formation, forming a superlattice; doping the superlattice with a rare earth element; depositing an electrode overlying the doped superlattice; and, forming an EL device.
- a p-doped/insulator/n-doped EL device is formed.
- the method then comprises: providing an n-type Si substrate; forming an initial p-type polysilicon layer overlying the initial SiO 2 layer; forming a superlattice of alternating layers of n and p-type polysilicon, with a final set of layers being n-type polysilicon overlaid by SiO 2 ; and, depositing a p-type electrode to form a p-i-n EL device.
- the polysilicon layers are formed using a chemical vapor deposition (CVD) process to deposit an amorphous silicon layer, and annealing.
- CVD chemical vapor deposition
- a DC-sputtering process deposits each amorphous silicon and SiO 2 layer, and following the formation of the superlattice, polysilicon is formed by annealing the amorphous silicon layers.
- the silicon dioxide layers can be formed by thermal annealing.
- FIG. 1 is a partial cross-sectional view of a superlattice nanocrystal silicon (Si)-silicon dioxide (SiO 2 ) electroluminescence (EL) device.
- FIG. 2 is a partial cross-sectional view of a PIN variation of the Si—SiO 2 EL device of FIG. 1 .
- FIG. 3 is a partial cross-sectional view of an NIP variation of the Si—SiO 2 EL device of FIG. 1 .
- FIG. 4 is another partial cross-sectional view of the present invention EL device.
- FIG. 5 shows the x-ray patterns of polysilicon thin films as deposited, and after post-annealing.
- FIG. 6 is a graph depicting the formation of nanocrystalline polysilicon after thermal oxidation.
- FIG. 7 is a graph depicting the film thickness of polysilicon as a function of deposition time.
- FIG. 8 is a graph depicting the oxidation thickness of polysilicon as a function of oxidation temperatures.
- FIG. 9 is a graph depicting polysilicon oxide thickness as a function of oxidation time.
- FIG. 10 shows the x-ray pattern of a superlattice Si—SiO2 structure with 5 layers of polysilicon deposition and oxidation, as a function of polysilicon deposition times.
- FIG. 11 is a flowchart depicting a method for forming a superlattice nanocrystal Si—SiO 2 EL device.
- FIG. 1 is a partial cross-sectional view of a superlattice nanocrystal silicon (Si)-silicon dioxide (SiO 2 ) electroluminescence (EL) device.
- the device 100 comprises a Si substrate 102 and an initial rare earth element-doped SiO 2 layer 104 overlying the substrate.
- An initial rare earth element-doped polysilicon layer 106 overlies the initial rare earth element-doped SiO 2 layer 104 .
- a rare earth element-doped SiO 2 layer 108 overlies the initial doped polysilicon layer 106 .
- This layering of polysilicon and silicon dioxide layers is repeated forming a superlattice 110 .
- An electrode 112 overlies the superlattice 110 .
- the EL device can have as many as 100, and as few as three layers, where the number of layers is defined as the total number of polysilicon layers between the substrate and the electrode. The operating voltage increases as the number of polysilicon layers increases.
- FIG. 2 is a partial cross-sectional view of a PIN variation of the Si—SiO 2 EL device of FIG. 1 .
- the Si substrate 102 is an n-type Si substrate.
- the initial doped polysilicon layer 106 is a p-type polysilicon layer.
- the superlattice 110 includes alternating layers of n and p-type doped polysilicon.
- the final set of layers 200 is an n-type polysilicon layer 202 overlaid by SiO 2 layer 204 .
- the electrode 112 is a p-type electrode, and a p-doped/insulator/n-doped (p-i-n) EL device is formed.
- Some examples of p-type electrode materials include p-Si, p-Ge, and p-GaN. However, the invention is not limited to any particular electrode materials.
- FIG. 3 is a partial cross-sectional view of an NIP variation of the Si—SiO 2 EL device of FIG. 1 .
- the Si substrate 102 is a p-type Si substrate.
- the initial doped polysilicon layer 106 is an n-type polysilicon layer.
- the superlattice 110 includes alternating layers of p and n-type doped polysilicon.
- the final set of layers 300 is a p-type polysilicon layer 302 overlaid by SiO 2 layer 304 .
- the electrode 112 is an n-type electrode, and the result is an n-doped/insulator/p-doped (n-i-p) EL device.
- Some examples of n-type electrode materials include ITO, InOx, ZnOx, and Al doped ZnOx. However, the invention is not limited to any particular electrode materials.
- each rare earth element-doped polysilicon layer i.e. layer 106
- Device efficiency can be improved by controlling the uniformity of the polysilicon thickness 120 between layers.
- the deviation in thickness between polysilicon layers in the superlattice is in the range of 1 to 10%.
- Each rare earth element-doped polysilicon layer includes crystalline grain sizes in the range of 0.5 and 30 nm.
- Each rare earth element-doped SiO 2 layer i.e., layer 104
- the polysilicon and SiO 2 layers are doped with a rare earth element such as Er, Tb, Yb, Pr, Nd, La, or Ce.
- the EL device is not limited to any particular rare earth doping element. There is a direct relationship between grain size and the EL wavelength. Reducing the grain size shifts the EL peak to a short wavelength. Increasing the variation in grain sizes, therefore, broadens EL peak.
- FIG. 4 is another partial cross-sectional view of the present invention EL device.
- the device comprises a superlattice structure of Si—SiO2 interfaces, so as to obtain a high density of Si—SiO2 interfaces that can be used in EL device applications.
- CVD is used to deposit a very thin polysilicon layer from 2-10 nm.
- a thermal oxidation process converts 10-80% of the polysilicon into silicon dioxide.
- a superlattice structure of Si—SiO2 can be obtained.
- a rare earth element, such as Er is implanted to make an Er-doped Si—SiO2 superlattice structure.
- CVD polysilicon deposition Particulars of the CVD polysilicon deposition, thermal oxidation processes, and Er implantation processes are shown in Table 1, 2 and 3, respectively.
- TABLE 1 CVD polysilicon deposition process conditions Deposition Silane flow Deposition temp. pressure Deposition time 40-200 sccm 500-600° C. 150-250 1-10 min. for mtorr each layer
- FIG. 5 shows the x-ray patterns of polysilicon thin films as deposited, and after post-annealing.
- the as-deposited silicon is amorphous.
- After post-annealing at a temperature of around 590° C. very small peaks appear at 28.2 and 47.1 degrees, meaning that the nucleation of polysilicon crystallization has occurred. With higher post-annealing temperatures, the counts of two peaks increase, meaning that the grain size of polysilicon has also increased.
- FIG. 6 is a graph depicting the formation of nanocrystalline polysilicon after post-annealing thermal oxidation.
- the grain size of polysilicon increases from a few nm, to 30 nm, as the thermal oxidation temperature increases from 560° C. to 850° C.
- the grain size of the superlattice or multi-layer Si/SiO2 structure is also controlled by polysilicon film thickness and the oxidation thickness.
- the grain sizes of polysilicon decrease as the film thickness of polysilicon decreases.
- the grain sizes of the polysilicon also decrease as the thermal oxidation thickness increases.
- FIG. 7 is a graph depicting the film thickness of polysilicon as a function of deposition time.
- FIG. 8 is a graph depicting the oxidation thickness of polysilicon as a function of oxidation temperatures.
- FIG. 9 is a graph depicting polysilicon oxide thickness as a function of oxidation time.
- the polysilicon deposition and oxidation time can be controlled to obtain the desired grain size of nano Si crystals.
- FIG. 10 shows the x-ray pattern of a superlattice Si—SiO2 structure with 5 layers of polysilicon deposition and oxidation, as a function of polysilicon deposition times.
- the thickness of the as-deposited polysilicon is about 5-16 nm for each layer, and the oxide thickness for each layer is about 3-6 nm.
- the final grain size of the nano Si crystals is about 5-12 nm, based upon the x-ray calculations.
- superlattice nanocrystal Si/SiO2 structures can be fabricated for electroluminescence (EL) device applications.
- EL electroluminescence
- FIG. 11 is a flowchart depicting a method for forming a superlattice nanocrystal Si—SiO 2 EL device. Although the method is depicted as a sequence of numbered steps for clarity, the numbering does not necessarily dictate the order of the steps. It should be understood that some of these steps may be skipped, performed in parallel, or performed without the requirement of maintaining a strict order of sequence.
- the method starts at Step 1100 .
- Step 1102 provides a Si substrate.
- Step 1104 forms an initial SiO 2 layer overlying the Si substrate.
- Step 1106 forms an initial polysilicon layer overlying the initial SiO 2 layer.
- Step 1108 forms a SiO 2 layer overlying the initial polysilicon layer.
- Step 1110 repeats the polysilicon and SiO 2 layer formation (Steps 1106 and 1108 ), forming a superlattice. Typically, a superlattice is formed with a total number of polysilicon layers in the range between 3 and 100.
- Step 1112 dopes the superlattice with a rare earth element.
- Step 1114 deposits an electrode overlying the doped superlattice.
- Step 1116 forms a final product, an EL device.
- Forming SiO 2 layers includes forming SiO 2 layers having a thickness in the range of 0.5 to 5 nm.
- providing the Si substrate in Step 1102 includes providing an n-type Si substrate.
- Forming the initial polysilicon layer in Step 1106 includes forming a p-type polysilicon layer.
- Repeating the polysilicon and SiO 2 layer formation in Step 1110 includes forming alternating layers of n and p-type polysilicon, with a final set of layers being n-type polysilicon overlaid by SiO 2 .
- Step 1114 deposits a p-type electrode, using a material such as p-Si, p-Ge, or p-GaN.
- Step 1116 forms a p-i-n EL device.
- providing the Si substrate in Step 1102 includes providing a p-type Si substrate.
- Forming the initial polysilicon layer in Step 1106 includes forming an n-type polysilicon layer.
- Repeating the polysilicon and SiO 2 layer formation in Step 1110 includes forming alternating layers of p and n-type polysilicon, with a final set of layers being p-type polysilicon overlaid by SiO 2 .
- Step 1114 deposits an n-type electrode from a material such as ITO, InOx, ZnOx, or Al-doped ZnOx.
- Step 1116 forms an n-i-p EL device.
- Step 1106 forming polysilicon layers (i.e., Step 1106 ) includes substeps.
- Step 1106 a uses a chemical vapor deposition (CVD) process to deposit an amorphous silicon layer.
- Step 1106 b anneals to form a polysilicon layer.
- the CVD process of Step 1106 a may include:
- silane at a rate in the range of 40 to 200 standard cubic centimeters per minute (sccm);
- Step 1106 forming polysilicon layers (i.e., Step 1106 ) includes other substeps.
- Step 1106 c uses a DC-sputtering process to deposit each amorphous silicon layer.
- Step 1106 d following the forming of the superlattice in Step 1110 , anneals the amorphous silicon layers, to form polysilicon layers.
- the DC sputtering process of Step 1106 c may include:
- a target material from a material such as undoped Si, p-type Si, or n-type Si;
- DC plasma power in the range of 50 to 300 W
- SiO2 layers may be formed (i.e., Step 1104 or 1108 ) by either a DC-sputtering process or by thermal oxidation. If a DC-sputtering process is used to deposit the SiO2 layers, the process may include:
- Forming the initial polysilicon layer in Step 1106 , or any polySi layer may include depositing silicon to a thickness in the range of 2 to 10 nanometers (nm). In one aspect, the deviation in thickness between the layers in the superlattice is in the range of 1 to 10%.
- the polysilicon typically has crystalline grain sizes in the range of 0.5 and 30 nm.
- the formation of SiO 2 layers may be performed by thermal annealing 10 to 80% of the underlying silicon layer.
- the thermal annealing of the underlying silicon may be accomplished by:
- Doping the superlattice with a rare earth element in Step 1112 includes: implanting the rare earth element at a voltage in the range of 10 to 500 keV; and, implanting the rare earth element at a dosage in the range of 1 ⁇ 10 13 to 1 ⁇ 10 16 ions per cm 2 .
- Step 1112 dopes with a rare earth element such as Er, Tb, Yb, Pr, Nd, La, or Ce.
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Abstract
Description
- 1. Field of the Invention
- This invention generally relates to integrated circuit (IC) fabrication and, more particularly, to a nanocrystalline superlattice silicon (Si)-silicon dioxide SiO2 electroluminescence (EL) device and light-emitting diode (LED) device.
- 2. Description of the Related Art
- An early paper in the field, published in Nature (440-444, 2000) by L. Pavesi, deals with silicon quantum dots. Since 2000, there have been numerous reports of optical gain in waveguide structures, EL, and light-emitting diode (LED) applications containing silicon quantum dots in the 2 to 4 nanometer (nm) range, prepared by different techniques. However, there are inconsistencies between the various experimental reports, and theoretical studies have not conclusively identified the mechanisms for optical gain.
- Many researchers have recently reported on the EL properties of Si rich silicon oxides. Keisuke Sato, from Tokyo Denki University, presented an interesting paper dealing with electroluminescence from Si-rich silicon oxide. To make the Si-rich silicon oxide thin films, he bonded small (5×5 mm) silicon pieces on a silicon dioxide target. Using radio frequency (RF) sputtering, a Si-rich silicon oxide, with silicon nano-particles of a size around 2.5 nm, was formed. The surface of Si rich silicon oxide was etched by HF and then post-annealed. Both the HF surface etching and the temperature of the post-annealing were reported to be key factors associated with the color of light emission. Red emission color was obtained from the HF treatment sample. Green emission color was observed from the sample post-annealed at 600° C., and blue for the sample post-annealed at a temperature of 900° C. From I-V measurements, Sato gave the light emission threshold voltages: 4.0V for red emission, 9.0V for green and 9.5V for blue emission. This data suggests very promising Si quantum dots EL and LED applications.
- Another interesting work comes from STMicroelectronics, Italy. Dr. Maria E. Castagna et al. presented a paper entitled “High efficiency light emission devices in silicon.” at the 2003 MRS spring meeting. The reported device consists of MOS structures with erbium (Er) implanted in the gate oxide. The device exhibited strong 1.54 μm (micrometer) electroluminescence at 300° k (room temperature) with a 10% external quantum efficiency, comparable to that of standard light emitting diodes using group III-V semiconductors. Emissions at different wavelengths have been achieved incorporating different rare earths (Ce, Tb, Yb, Pr) in the gate dielectric. The external quantum efficiency depends on the rare earth ions incorporated, and ranges from 10% (for a Tb doped MOS) to 0.1% (for an Yb doped MOS). Much more stable light emitting MOS devices have been fabricated using Er-doped SRO (Si-rich silicon oxide) films as the gate dielectric, but the external quantum efficiency is reduced to 0.2%. With respect to the light emission mechanism, it is thought that Er pumping occurs partly due to the impact of hot electrons, and partly by energy transfer from the Si nanostructures to the rare earth ions, depending on the Si excess in the film.
- Dr. Pasquarello has proposed a theory for the photoemission associated with a Si—SiO2 interface. According to the theory, Si 2p core-level shifts occur at the Si(001)-SiO2, and depend linearly on nearest-neighbor oxygen atoms. Second nearest-neighbor effects turn out to be negligibly small. Therefore, an efficient photoemission spectra requires that all Si oxidation states be present at the interface. Based on this theory, the making of a high density Si—SiO2 interface is a critical issue for EL device applications.
- It would be advantageous if a more efficient, easy to fabricate, EL device could be made based upon a high density Si—SiO2 interface.
- It would be advantageous the density of a Si—SiO2 interface could be increased by using a multi-layer Si—SiO2 superlattice.
- The present invention describes processes for the fabrication of a superlattice nanocrystalline Si and SiO2 structures for EL and LED device applications. Technologies are presented for making a multi-layer Si—SiO2 superlattice structure using CVD polysilicon deposition, thermal oxidation, and rare earth element implantation processes.
- Accordingly, a method is provided for forming a superlattice nanocrystal Si—SiO2 EL device. The method comprises: providing a Si substrate; forming an initial SiO2 layer overlying the Si substrate; forming an initial polysilicon layer overlying the initial SiO2 layer; forming SiO2 layer overlying the initial polysilicon layer; repeating the polysilicon and SiO2 layer formation, forming a superlattice; doping the superlattice with a rare earth element; depositing an electrode overlying the doped superlattice; and, forming an EL device.
- In one aspect, a p-doped/insulator/n-doped EL device is formed. The method then comprises: providing an n-type Si substrate; forming an initial p-type polysilicon layer overlying the initial SiO2 layer; forming a superlattice of alternating layers of n and p-type polysilicon, with a final set of layers being n-type polysilicon overlaid by SiO2; and, depositing a p-type electrode to form a p-i-n EL device.
- In one aspect, the polysilicon layers are formed using a chemical vapor deposition (CVD) process to deposit an amorphous silicon layer, and annealing. Alternately, a DC-sputtering process deposits each amorphous silicon and SiO2 layer, and following the formation of the superlattice, polysilicon is formed by annealing the amorphous silicon layers. As an alternative to the DC-sputtering process, the silicon dioxide layers can be formed by thermal annealing.
- Additional details of the above-described method, and a superlattice nanocrystal Si—SiO2 EL device are provided below.
-
FIG. 1 is a partial cross-sectional view of a superlattice nanocrystal silicon (Si)-silicon dioxide (SiO2) electroluminescence (EL) device. -
FIG. 2 is a partial cross-sectional view of a PIN variation of the Si—SiO2 EL device ofFIG. 1 . -
FIG. 3 is a partial cross-sectional view of an NIP variation of the Si—SiO2 EL device ofFIG. 1 . -
FIG. 4 is another partial cross-sectional view of the present invention EL device. -
FIG. 5 shows the x-ray patterns of polysilicon thin films as deposited, and after post-annealing. -
FIG. 6 is a graph depicting the formation of nanocrystalline polysilicon after thermal oxidation. -
FIG. 7 is a graph depicting the film thickness of polysilicon as a function of deposition time. -
FIG. 8 is a graph depicting the oxidation thickness of polysilicon as a function of oxidation temperatures. -
FIG. 9 is a graph depicting polysilicon oxide thickness as a function of oxidation time. -
FIG. 10 shows the x-ray pattern of a superlattice Si—SiO2 structure with 5 layers of polysilicon deposition and oxidation, as a function of polysilicon deposition times. -
FIG. 11 is a flowchart depicting a method for forming a superlattice nanocrystal Si—SiO2 EL device. -
FIG. 1 is a partial cross-sectional view of a superlattice nanocrystal silicon (Si)-silicon dioxide (SiO2) electroluminescence (EL) device. Thedevice 100 comprises aSi substrate 102 and an initial rare earth element-doped SiO2 layer 104 overlying the substrate. An initial rare earth element-dopedpolysilicon layer 106 overlies the initial rare earth element-doped SiO2 layer 104. Then, a rare earth element-doped SiO2 layer 108 overlies the initial dopedpolysilicon layer 106. This layering of polysilicon and silicon dioxide layers is repeated forming asuperlattice 110. Anelectrode 112 overlies thesuperlattice 110. The EL device can have as many as 100, and as few as three layers, where the number of layers is defined as the total number of polysilicon layers between the substrate and the electrode. The operating voltage increases as the number of polysilicon layers increases. -
FIG. 2 is a partial cross-sectional view of a PIN variation of the Si—SiO2 EL device ofFIG. 1 . TheSi substrate 102 is an n-type Si substrate. The initial dopedpolysilicon layer 106 is a p-type polysilicon layer. Thesuperlattice 110 includes alternating layers of n and p-type doped polysilicon. The final set oflayers 200 is an n-type polysilicon layer 202 overlaid by SiO2 layer 204. Theelectrode 112 is a p-type electrode, and a p-doped/insulator/n-doped (p-i-n) EL device is formed. Some examples of p-type electrode materials include p-Si, p-Ge, and p-GaN. However, the invention is not limited to any particular electrode materials. -
FIG. 3 is a partial cross-sectional view of an NIP variation of the Si—SiO2 EL device ofFIG. 1 . TheSi substrate 102 is a p-type Si substrate. The initial dopedpolysilicon layer 106 is an n-type polysilicon layer. Thesuperlattice 110 includes alternating layers of p and n-type doped polysilicon. The final set oflayers 300 is a p-type polysilicon layer 302 overlaid by SiO2 layer 304. Theelectrode 112 is an n-type electrode, and the result is an n-doped/insulator/p-doped (n-i-p) EL device. Some examples of n-type electrode materials include ITO, InOx, ZnOx, and Al doped ZnOx. However, the invention is not limited to any particular electrode materials. - Returning to
FIG. 1 , (the following discussion is equally applicable toFIGS. 2 and 3 ), each rare earth element-doped polysilicon layer (i.e. layer 106) has athickness 120 in the range of 2 to 10 nanometers (nm). Device efficiency can be improved by controlling the uniformity of thepolysilicon thickness 120 between layers. In one aspect, the deviation in thickness between polysilicon layers in the superlattice is in the range of 1 to 10%. - Each rare earth element-doped polysilicon layer includes crystalline grain sizes in the range of 0.5 and 30 nm. Each rare earth element-doped SiO2 layer (i.e., layer 104) has a
thickness 122 in the range of 0.5 to 5 nm. Typically, the polysilicon and SiO2 layers are doped with a rare earth element such as Er, Tb, Yb, Pr, Nd, La, or Ce. However, the EL device is not limited to any particular rare earth doping element. There is a direct relationship between grain size and the EL wavelength. Reducing the grain size shifts the EL peak to a short wavelength. Increasing the variation in grain sizes, therefore, broadens EL peak. -
FIG. 4 is another partial cross-sectional view of the present invention EL device. The device comprises a superlattice structure of Si—SiO2 interfaces, so as to obtain a high density of Si—SiO2 interfaces that can be used in EL device applications. In one aspect of the fabrication process, CVD is used to deposit a very thin polysilicon layer from 2-10 nm. Then, a thermal oxidation process converts 10-80% of the polysilicon into silicon dioxide. Repeating the polysilicon CVD deposition and thermal oxidation processes, a superlattice structure of Si—SiO2 can be obtained. Then, a rare earth element, such as Er, is implanted to make an Er-doped Si—SiO2 superlattice structure. Particulars of the CVD polysilicon deposition, thermal oxidation processes, and Er implantation processes are shown in Table 1, 2 and 3, respectively.TABLE 1 CVD polysilicon deposition process conditions Deposition Silane flow Deposition temp. pressure Deposition time 40-200 sccm 500-600° C. 150-250 1-10 min. for mtorr each layer -
TABLE 2 thermal oxide process conditions Oxygen Nitrogen Oxidation Oxidation flow flow temp. pressure Oxidation time 1.6 SLPM 8 SLPM 700-1100° C. atmosphere 5-60 min. for each layer -
TABLE 3 Er implantation process conditions Implantation Implantation voltage Er Dose Angle 10-500 keV 1 × 1013-1 × 1016 ions/cm2 -
FIG. 5 shows the x-ray patterns of polysilicon thin films as deposited, and after post-annealing. The as-deposited silicon is amorphous. After post-annealing at a temperature of around 590° C., very small peaks appear at 28.2 and 47.1 degrees, meaning that the nucleation of polysilicon crystallization has occurred. With higher post-annealing temperatures, the counts of two peaks increase, meaning that the grain size of polysilicon has also increased. -
FIG. 6 is a graph depicting the formation of nanocrystalline polysilicon after post-annealing thermal oxidation. The grain size of polysilicon increases from a few nm, to 30 nm, as the thermal oxidation temperature increases from 560° C. to 850° C. The grain size of the superlattice or multi-layer Si/SiO2 structure is also controlled by polysilicon film thickness and the oxidation thickness. The grain sizes of polysilicon decrease as the film thickness of polysilicon decreases. The grain sizes of the polysilicon also decrease as the thermal oxidation thickness increases. -
FIG. 7 is a graph depicting the film thickness of polysilicon as a function of deposition time. -
FIG. 8 is a graph depicting the oxidation thickness of polysilicon as a function of oxidation temperatures. -
FIG. 9 is a graph depicting polysilicon oxide thickness as a function of oxidation time. The polysilicon deposition and oxidation time can be controlled to obtain the desired grain size of nano Si crystals. -
FIG. 10 shows the x-ray pattern of a superlattice Si—SiO2 structure with 5 layers of polysilicon deposition and oxidation, as a function of polysilicon deposition times. The thickness of the as-deposited polysilicon is about 5-16 nm for each layer, and the oxide thickness for each layer is about 3-6 nm. The final grain size of the nano Si crystals is about 5-12 nm, based upon the x-ray calculations. Using these technologies, superlattice nanocrystal Si/SiO2 structures can be fabricated for electroluminescence (EL) device applications. -
FIG. 11 is a flowchart depicting a method for forming a superlattice nanocrystal Si—SiO2 EL device. Although the method is depicted as a sequence of numbered steps for clarity, the numbering does not necessarily dictate the order of the steps. It should be understood that some of these steps may be skipped, performed in parallel, or performed without the requirement of maintaining a strict order of sequence. The method starts atStep 1100. -
Step 1102 provides a Si substrate.Step 1104 forms an initial SiO2 layer overlying the Si substrate.Step 1106 forms an initial polysilicon layer overlying the initial SiO2 layer.Step 1108 forms a SiO2 layer overlying the initial polysilicon layer.Step 1110 repeats the polysilicon and SiO2 layer formation (Steps 1106 and 1108), forming a superlattice. Typically, a superlattice is formed with a total number of polysilicon layers in the range between 3 and 100.Step 1112 dopes the superlattice with a rare earth element.Step 1114 deposits an electrode overlying the doped superlattice.Step 1116 forms a final product, an EL device. Forming SiO2 layers (i.e.,Steps - In one aspect, providing the Si substrate in
Step 1102 includes providing an n-type Si substrate. Forming the initial polysilicon layer inStep 1106 includes forming a p-type polysilicon layer. Repeating the polysilicon and SiO2 layer formation inStep 1110 includes forming alternating layers of n and p-type polysilicon, with a final set of layers being n-type polysilicon overlaid by SiO2. Then,Step 1114 deposits a p-type electrode, using a material such as p-Si, p-Ge, or p-GaN.Step 1116 forms a p-i-n EL device. - In another aspect, providing the Si substrate in
Step 1102 includes providing a p-type Si substrate. Forming the initial polysilicon layer inStep 1106 includes forming an n-type polysilicon layer. Repeating the polysilicon and SiO2 layer formation inStep 1110 includes forming alternating layers of p and n-type polysilicon, with a final set of layers being p-type polysilicon overlaid by SiO2. Then,Step 1114 deposits an n-type electrode from a material such as ITO, InOx, ZnOx, or Al-doped ZnOx.Step 1116 forms an n-i-p EL device. - In a different aspect, forming polysilicon layers (i.e., Step 1106) includes substeps.
Step 1106 a uses a chemical vapor deposition (CVD) process to deposit an amorphous silicon layer.Step 1106 b anneals to form a polysilicon layer. The CVD process ofStep 1106 a may include: - flowing silane at a rate in the range of 40 to 200 standard cubic centimeters per minute (sccm);
- heating the substrate to a temperature in the range of 500 to 600° C.;
- creating an atmospheric pressure in the range of 150 to 250 millitorr (mtorr); and,
- depositing silicon for a time duration in the range of 1 to 10 minutes.
- Alternately, forming polysilicon layers (i.e., Step 1106) includes other substeps.
Step 1106 c uses a DC-sputtering process to deposit each amorphous silicon layer.Step 1106 d, following the forming of the superlattice inStep 1110, anneals the amorphous silicon layers, to form polysilicon layers. The DC sputtering process ofStep 1106 c may include: - providing a target material from a material such as undoped Si, p-type Si, or n-type Si;
- flowing Ar with deposition pressure in the range of 5 mtorr to 10 mtorr;
- using a DC plasma power in the range of 50 to 300 W;
- heating the substrate to a temperature in the range of 50 to 300° C.; and,
- depositing for a time duration in the range of 0.5 to 10 minutes.
- When the DC-sputtering process is used to deposit Si, SiO2 layers may be formed (i.e.,
Step 1104 or 1108) by either a DC-sputtering process or by thermal oxidation. If a DC-sputtering process is used to deposit the SiO2 layers, the process may include: - providing an undoped Si target;
- flowing oxygen at partial pressure in the range of 5 to 30%, with Ar;
- supplying DC plasma power in the range of 50 to 300 W;
- heating the substrate to a temperature in the range of 50 to 300° C.; and,
- depositing for a time duration in the range of 1 to 10 minutes.
- Forming the initial polysilicon layer in
Step 1106, or any polySi layer (i.e., Step 1110) may include depositing silicon to a thickness in the range of 2 to 10 nanometers (nm). In one aspect, the deviation in thickness between the layers in the superlattice is in the range of 1 to 10%. The polysilicon typically has crystalline grain sizes in the range of 0.5 and 30 nm. - The formation of SiO2 layers (i.e.,
Steps 1108 or 1110) may be performed bythermal annealing 10 to 80% of the underlying silicon layer. The thermal annealing of the underlying silicon may be accomplished by: - flowing oxygen at a rate of about 1.6 standard liters per minute (SLPM);
- flowing nitrogen at a rate of about 8 SLPM;
- heating the substrate to a temperature in the range of 700 to 1100° C.; and,
- oxidizing for time duration in the range of 5 to 60 minutes.
- Doping the superlattice with a rare earth element in
Step 1112 includes: implanting the rare earth element at a voltage in the range of 10 to 500 keV; and, implanting the rare earth element at a dosage in the range of 1×1013 to 1×1016 ions per cm2.Step 1112 dopes with a rare earth element such as Er, Tb, Yb, Pr, Nd, La, or Ce. - A Si-silicon oxide nanocrystalline superlattice EL device and associated fabrication process have been presented. Specific process details and materials have been presented as examples, to illustrate the invention. However, the invention is not limited to merely these examples. Other variations and embodiments of the invention will occur to those skilled in the art.
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