Low-Temperature Formation Of Thin-Film Structures
20170316937 · 2017-11-02
Inventors
Cpc classification
H01L21/02667
ELECTRICITY
H01L21/02422
ELECTRICITY
H01L21/02211
ELECTRICITY
H01L21/0262
ELECTRICITY
H01L29/66757
ELECTRICITY
H01L29/78603
ELECTRICITY
H01L27/1285
ELECTRICITY
International classification
Abstract
Methods for low-temperature formation of one or more thin-film semiconductor structures on a substrate that include the steps of, forming a (poly)silane layer over a substrate, transforming one or more parts of the (poly)silane layer in one or more thin-film solid-state semiconductor structures, by exposing the one or more parts with light from an
Claims
1. A method for low-temperature formation of one or more thin-film semiconductor structures on a substrate comprising: forming a (poly)silane layer over a substrate; transforming one or more parts of said (poly)silane layer in one or more thin-film solid-state semiconductor structures by exposing said one or more parts with light from an UV source.
2. The method according to claim 1 wherein selectively transforming one or more parts of said (poly)silane layer comprises: illuminating a mask with light from said UV source for transferring a pattern on said mask onto said (poly)silane layer.
3. The method according to claim 1 wherein transforming one or more parts of said (poly)silane layer comprises: exposing a first part of said (poly)silane layer with light of a first fluence for transforming said first part into a semiconductor with a first crystallinity; exposing a second part of said (poly)silane layer with light of a second fluence for transforming said second part into a semiconductor with a second crystallinity.
4. The method according to claim 1 wherein transforming one or more parts of said (poly)silane layer comprises: exposing said one or more parts of said (poly)silane layer by moving a (pulsed) UV light beam of a predetermined size over said (poly)silane layer.
5. The method according to claim 1 further comprising: transforming (poly)silane of said layer that is not transformed in a thin-film semiconductor structure into a semiconductor oxide by exposing said (poly)silane to oxygen.
6. The method according to claim 1 further comprising: embedding said thin-film solid-state semiconductor structures in an semiconductor oxide by exposing said (poly)silane comprising said thin-film solid-state semiconductor structures to oxygen.
7. The method according to claim 6 further comprising forming a conducting (gate) layer over at least part of at least one of said embedded thin-film solid-state semiconductor structures.
8. The method according to claim 1 wherein said UV source is configured for generating one or more wavelengths within the range between 100 and 450 nm.
9. The method according to claim 1 wherein the energy density (fluence) of said UV light source is selected such that said transformation of said (poly)silane layer takes place without heating the temperature of the substrate.
10. The method according to claim 1 wherein transforming one or more parts of said of said (poly)silane layer comprises: exposing said one or more parts of said (poly)silane layer to UV light from a (pulsed) laser.
11. The method according to claim 1 wherein transforming one or more parts of said of said (poly)silane layer comprises: exposing said one or more parts of (poly)silane layer to light from a LED array, having an irradiance selected between 40 and 400 mW/cm2.
12. The method according to claim 1 wherein said (poly)silane layer comprises a silane compound defined by the general formula Si.sub.nX.sub.m, wherein X is a hydrogen; n is an integer of 5 or greater and m is an integer equal to n, 2n−2, 2n or 2n+1.
13. The method according to claim 1 wherein said (poly)silane layer is formed on said substrate by applying a substantially pure liquid (poly)silane on said substrate.
14. The method according to claim 1 wherein said substrate is a polymer-based substrate, a paper or cellulose based substrate, a fibre-based substrate, PEN or PET or derivatives thereof.
15. The method according to claim 1 wherein said (poly)silane layer is formed over said substrate using a printing technique.
16. The method according to claim 15 wherein said printing technique is used to form a patterned (poly)silane layer on said substrate.
17. The method according to claim 1 wherein a coating technique is used for forming a continuous (poly)silane layer on said substrate.
18. Use of the method according to claim 1, in the manufacturer of a semiconducting device.
19. A thin-film semiconductor structure comprising: a substrate; a continuous thin-film layer on said substrate wherein said thin-film layer comprises one or more thin-film semiconductor structures and one or more thin-film (poly)silane structures and wherein the top surface of said continuous thin-film layer is substantially planar.
20. The thin-film structure according to claim 19 wherein a first semiconductor structure of said one or more thin-film semiconductor structures has a first crystallinity and wherein a second semiconductor structure of said one or more thin-film semiconductor structures has a second crystallinity.
21. A thin-film semiconductor structure comprising: a substrate; a continuous thin-film layer on said substrate wherein said thin-film layer comprises one or more thin-film semiconductor structures, and one or more thin-film patterned semiconductor oxide structures wherein said one or more thin-film semiconductor structures are embedded in said one or more thin-film semiconductor oxide structures and wherein the top surface of said continuous thin-film layer is substantially planar.
22. The method according to claim 1 further comprising: transforming (poly)silane of said layer that is not transformed in a thin-film semiconductor structure into a semiconductor oxide by exposing said (poly)silane to ozone.
23. The method according to claim 1 further comprising: embedding said thin-film solid-state semiconductor structures in an semiconductor oxide by exposing said (poly)silane comprising said thin-film solid-state semiconductor structures to ozone.
24. The method according to claim 9 wherein the energy density (fluence) of said UV light source is selected such that said transformation of said (poly)silane layer takes place without heating the substrate temperature to temperatures higher than 300° C.
25. The method according to claim 10 wherein transforming one or more parts of said (poly)silane layer comprises: exposing said one or more parts of said (poly)silane layer to UV light from a (pulsed) laser having energy density (fluence) between 50 and 400 mJ/cm2.
26. The method according to claim 11 wherein transforming one or more parts of said (poly)silane layer comprises: exposing said one or more parts of (poly)silane layer to light from the light of said a LED array.
27. The method according to claim 12 wherein said (poly)silane layer comprises neopentasilane.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0031]
[0032]
[0033]
[0034]
[0035]
[0036]
[0037]
[0038]
DETAILED DESCRIPTION
[0039]
[0040] Alternatively, a printing technique such gravure printing, screen printing, flexographic/letterpress printing, ink jet printing and/or offset printing may be used to apply a silane layer the substrate. In that case, the silane layer may be have a particular printing pattern. For example, when using an ink jet printer for depositing a silane layer on the substrate, the ink jet printer may print a particular patterned silane layer on the substrate.
[0041] Preferably, the substrate may comprise a flexible plastic substrate material including for example a polyamide, polyethylene naphthalate (PEN) and/or polyethylene terephthalate (PET). Alternatively and/or in addition, the substrate may comprise a flexible substrate material including cellulose-based material and/or a (woven or a non-woven) fibre-based material.
[0042] In an embodiment, the liquid silane may comprise cyclopentasilane (CPS) Si.sub.5H.sub.10. In an embodiment, the CPS may be irradiated with UV radiation for a predetermined time. The UV radiation may be used in order to break the CPS rings and to transform at least part of the CPS in (low-order) polysilanes, which are soluble in the CPS. Hence, by UV irradiating the CPS coating a coating may be formed comprising polysilane or a mixture of polysilane and CPS (a cyclic silane). For the purpose of this disclosure, a polysilane coating or a mixed polysilane-cyclic silane coating will be referred to as a polysilane coating.
[0043] In an embodiment, the CPS may be irradiated with an UV light source for generating UV light having an intensity selected between 1 and 100 mW, preferably between 2 and 50 mW, more preferably between 5 and 20 mW. Depending on the selected intensity and the desired degree of polymerization, the coating may be exposed to UV light for a period between 1 and 100 minutes, preferably between 2 and 50 minutes, more preferably between 5 and 40 minutes. The polymerization process transforms the CPS into a polysilane coating or a mixed polysilane-CPS coating that is more viscous and more stable for handing in subsequent processing steps. Moreover, the formation of polysilane increases the boiling temperature of the coating so that the coating can be annealed at temperatures higher than the boiling temperature of CPS (which is around 194° C.).
[0044] The thickness of the polysilane thin-film layer may be selected between 50 and 5000 nm, preferably between 50 and 4000 nm, more preferably between 50 and 2000 nm or between 50 and 1000 nm.
[0045] While the examples in this application are described with reference to cyclopentasilane (CPS) Si.sub.5H.sub.10, the invention is by no limited to this material. In particular, the invention may be used with liquid semiconductor precursors comprising one or more silane compounds. In an embodiment, a silane compound may be represented by the general formula Si.sub.nX.sub.m, wherein X is a hydrogen; n is preferably an integer of 5 or greater and is more preferably an integer between 5 and 20; m is preferably an integer of n, 2n−2, 2n or 2n+1; wherein part of the hydrogen may be replace by a halogen.
[0046] Examples of such silane compounds are described in detail in EP1087428, which is hereby incorporated by reference into this application. Examples of the compounds of m=2n+2 include silane hydrides, such as trisilane, tetrasilane, pentasilane, hexasilane, and heptasilane, and substituted compounds thereof in which hydrogen atoms are partially or completely replaced with halogen atoms. Examples of m=2n include monocyclic silicon hydride compounds, such as cyclotrisilane, cyclotetrasilane, cyclopentasilane, silylcyclopentasilane, cyclohexasilane, silylcyclohexasilane, and cycloheptasilane; and halogenated cyclic silicon compounds thereof in which hydrogen atoms are partially or completely replaced with halogen atoms, such as hexachlorocyclotrisilane, trichlorocyclotrisilane, coctachlorocyclotetrasilane, tetrachlorocyclotetrasilane, decachlorocyclopentasilane, pentachlorocyclopentasilane, dodecachlorocyclohexasilane, hexachlorocyclohexasilane, tetradecachlorocycloheptasilane, heptachlorocycloheptasilane, hexabromocyclotrisilane, tribromocyclotrisilane, pentabromocyclotrisilane, tetrabromocyclotrisilane, octabromocyclotetrasilane, tetrabromocyclotetrasilane, decabromocyclopentasilane, pentabromocyclopentasilane, dodecabromocyclohexasilane, hexabromocyclohexasilane, tetradecabromocycloheptasilane, and heptabromocycloheptasilane. Examples of compounds of m=2n-2 include dicyclic silicon hydride compounds, such as 1,1′-biscyclobutasilane, 1,1′-biscyclopentasilane, 1,1′-biscyclohexasilane, 1,1′-biscycloheptasilane, 1,1′-cyclobutasilylcyclopentasilane, 1,1′-cyclobutasilylcyclohexasilane, 1,1′-cyclobutasilylcycloheptasilane, 1,1′-cyclopentasilylcyclohexasilane, 1,1′-cyclopentasilylcycloheptasilane, 1,1′-cyclohexasilylcycloheptasilane, spiro[2,2]pentasilane, spiro[3,3]heptasilane, spiro[4,4]nonasilane, spiro[4,5]decasilane, spiro[4,6]undecasilane, spiro[5,5]undecasilane, spiro[5,6]dodecasilane, and spiro[6,6]tridecasilane; substituted silicon compounds in which hydrogen atoms are partly or completely replaced with SiH3 groups or halogen atoms. Moreover, examples of compounds of m=n include polycyclic silicon hydride compounds, such as Compounds 1 to 5 represented by the following formulae, arid substituted silicon compounds thereof in which hydrogen atoms are partially or completely replaced with SiH3 groups or halogen atoms. These compounds may be used as a mixture of two or more types.
[0047] In an embodiment, the liquid silane compound may comprise a cyclic silane, such as cyclopentasilane (CPS) Si.sub.5H.sub.10 and/or cyclohexasilane (CHS) Si.sub.6H.sub.12. In another embodiment, the liquid silane compound may comprise neopentasilane.
[0048] In an embodiment, a substantially pure liquid silane compound or a mixture of at least two substantially pure liquid silane compounds may be used in the formation of a polysilane coating on a substrate. In an embodiment “substantially pure” may refer to a purity level of a liquid semiconducting precursor of 94%, 96%, 98% or higher than 99%.
[0049] The polysilane coating may then be transformed into a solid-state silicon layer by exposing the coating to UV light. In an embodiment, polysilane coating may be transformed directly, i.e. without any thermal annealing step (e.g. a hot plate anneal), in silicon by exposing the polysilane layer to UV radiation for a predetermined time.
[0050]
[0051] The laser light has a wavelength selected within the UV range, e.g. between 100 and 450 nm, preferably between 200 and 400 nm. Examples of such UV laser include but are not limited to excimer lasers, YAG lasers, argon lasers, etc. The
[0052] UV laser may be configured to transmit short pulses of laser light in the UV spectrum. In an embodiment, the pulse width may be selected between 5 and 500 nm. In another embodiment, a laser pulse may have an energy density (fluence) selected between 20 and 1000 mJ/cm2, preferably 25 and 500 mJ/cm2, more preferably between 50 and 400 mJ/cm2.
[0053] Hence, in an embodiment, UV laser light pulses may be used to directly transform the polysilane into silicon. As will be shown hereunder in greater detail, depending on the fluence and the number of pulses the polysilane layer may be transformed in different types of silicon layers, including amorphous, microcrystalline, nanocrystalline and/or polycrystalline silicon.
[0054]
[0055] In case patterned polysilane layer formed on the substrate, e.g. using a (ink jet) printing technique, patterned silicon structures may be realized on the basis of the low-temperature process depicted in
[0056]
[0057] The associated Raman spectrum shows the formation of a high quality polysilicon layer. The AFM measurements indicate an average grain size of 124 nm and an average roughness of 23 nm. The grain size can be controlled by the number of pulses.
[0058]
[0059] When using pulsed laser light in the UV range, the layers can be effectively instantaneously transformed into solid-state silicon on the basis of only one or more very short pulses. Such laser pulses may have a pulse width within 10-500 ns, hence the transformation of the (poly)silane compounds occurs at a very short time-scale, thus providing a very fast and efficient process of forming silicon on the basis of a (poly)silane coating. Hence, the time for transforming the coating depends on the pulse width and the number of pulses that are used for the transformation. Hence, when using only one pulse the (poly)silane coating may be transformed into a solid state silicon within 10-500 ns. Alternatively, when using multiple pulses, the transformation time approximately equals the pulse width times the number of pulses.
[0060] Similar Raman spectra were obtained when exposing polysilane coatings to UV radiation originating from an UV LED array as described with reference to
[0061] It has been surprisingly found that one or more layers of silane compounds (e.g. coating of one or more silane compounds) can be directly transformed by UV light into silicon without thermally annealing the substrate (either before or during the transformation). Direct transformation of the (poly)silane into silicon has been achieved by exposing the layer to UV laser pulses of a predetermined energy density to UV LED light of a predetermined irradiance. Because the (poly)silane is directly and substantially instantaneously transformed into amorphous or crystalline silicon the substrate does not need to be subjected to annealing temperatures that are higher than the maximum handling temperature of the substrate, in particular plastic substrates such as polyamide, PEN or PET. Such process is very suitable for using in high throughput processing.
[0062] The low-temperature process based on pulse laser light allows direct, very fast (even single pulse) transformation of the polysilane coating into a silicon coating. The UV LED based process allows a simple and cheap way of directly transforming the polysilane coating into a silicon coating. In any way, both processes do not require high-vacuum conditions and are compatible with roll-to-roll processing.
[0063] The low-temperature solution-based process described with reference to
[0064] In a further embodiment, the solution-based low-temperature process described above may also be used for forming silicon-dioxide (SiO.sub.2) on a flexible substrate. In this process, polysilane may be coated onto a substrate in a similar way as described with reference to
[0065] The oxidation process may be accelerated by heating the substrate up to a temperature that is below the maximum handling temperature of the substrate material. In an embodiment, the substrate may be heated to a temperature between 100 and 300° C. In another embodiment, the substrate may be heated up to a temperature selected between 100 and 250° C. In yet another embodiment, the substrate may be heated up to a temperature selected between 100 and 200° C.
[0066] Alternatively and/or in addition, the oxidation process may be accelerated by exposing the polysilane layer to UV light of an UV source during the oxidation step. In particular, during and/or after the oxidation process, the polysilane layer may be exposed to UV light. Preferably, an UV LED system as described with reference to
[0067]
[0068] The CPS was polymerized into a polysilane solution by exposing the layer to UV light for 30 minutes at a temperature of 100° C. Thereafter the polysilane coating was directly crystallized by exposing the coating to pulsed laser light of an XeCl excimer laser (308 nm, 28ns). As shown in the Raman spectra of
[0069] On the basis of the low-temperature formation process described above, silicon structures of different shapes can be formed directly into the polysilane layer without using photoresist and/or a structured substrate. Typically, the fluence of the pulse is selected between 10 and 1000 mW/cm2, preferably 20 and 800 mW/cm2, more preferably between 40 and 400 mW/cm2 and the number of pulses is selected between 1-400, preferably 1 and 200. In some embodiments, exposure is realized by selecting a first number of pulses of a first fluence and a second number of pulses of a second fluence.
[0070] As will be shown hereunder in more detail, crystalline structures with small feature size can be formed in the polysilane layer in a very efficient way.
[0071]
[0072] The projection exposure system may comprise an exposure UV light source 510 comprising an UV laser 512, e.g. an excimer laser, for exposing a mask 518 with ultraviolet light 516 and an optical system 514,508 that is configured to transfer a mask pattern into the polysilane layer 504. The optical system may comprise optical elements, e.g. an optical integrator (a homogenizer), field stops, a condenser lens, etc. so that the mask is illuminated with a homogenous light beam and so that light passing the mask is reduced and projected onto the surface of the polysilane coating under a certain projection magnification.
[0073] The substrate (wafer) 502 comprising the polysilane coating 504 may be placed in holder that is positioned in line with the optical axis 522 (z-axis) of the optical system. Both the mask and the substrate may be mounted on a holder that is movable in the plane that is perpendicular to the optical axis (i.e. the plane defined by the x-axis and y-axis) so during the exposure system different exposure patterns of the mask can be used to exposure different areas of the polysilane layer. Light that exits the optical system at the exit of the optical system illuminates areas 520 in the polysilane coating so that these areas are transformed into crystalline silicon. This way, crystalline silicon areas are formed in the polysilane coating that have a shape that is determined by the mask pattern.
[0074] State of the art UV projection exposure systems as shown in
[0075]
[0076] The light source may generate UV light 530 for illuminating a mask 532 comprising non-transparent regions 534 and transparent regions 536. Optionally, the light that passes through the mask may be projected by an optical system 538 on the polysilane layer. Light that passes the mask illuminates areas 520 in the polysilane coating so that these areas are transformed into crystalline silicon. This way patterns on the mask can be transferred onto the polysilane layer wherein the areas of the polysilane layers that are exposed to the light will be directly transformed into silicon. The UV LED based projection exposure allows a simple and cheap way of transforming the polysilane coating directly into a silicon coating.
[0077] Hence, the projection exposure systems of
[0078]
[0079] Thereafter, the layer comprising the polysilane areas and the silicon areas may be subjected to an oxidation step as shown in
[0080] The oxidation process may be accelerated by heating the substrate up to a temperature that is below the maximum handling temperature of the substrate material. In an embodiment, the substrate may be heated to a temperature between 100 and 300° C. In another embodiment, the substrate may be heated up to a temperature selected between 100 and 250° C. In yet another embodiment, the substrate may be heated up to a temperature selected between 100 and 200° C.
[0081] Alternatively and/or in addition, the oxidation process may be accelerated by exposing the layer to UV light of an UV source 506 during the oxidation step. In particular, during and/or after the oxidation process, the polysilane layer may be exposed to UV light. Preferably, an UV LED system as described with reference to
[0082] In an embodiment, the UV LED array may be configured to generate an irradiance selected between 10 and 1000 mW/cm2, preferably 20 and 800 mW/cm2, more preferably between 40 and 400 mW/cm2. During exposure, the UV LED array may be positioned at a predetermined distance from the substrate surface. The distance may be selected between 10 and 1000 mm, preferably between 25 and 100 mm.
[0083] Hence, after the oxidation process, a thin-film structure is formed on the substrate wherein the silicon structure is embedded in the silicon oxide. The embedded silicon/silicon oxide structure as shown in
[0084] Based on further TFT processing steps the embedded silicon/silicon oxide structure may be processed into a transistor structure comprising a channel 614 that is in electrical contact to a source and drain contacts 622,624. Doped regions in the 628 in the silicon channel structure allow Ohmic contact to the source and drain contacts. Further, the silicon oxide layer that was formed by oxidizing the polysilane into silicon oxide electrically isolates the silicon channel from other parts of the device. A polysilicon gate 620 may be formed on top of the thin silicon oxide gate isolation layer that was formed during the oxidation of the silicon/polysilane structure (as shown in
[0085] The embedded silicon/silicon oxide structure as shown in
[0086] Hence, as shown in
[0087]
[0088]
[0089] The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the singular forms “a,” “an,” and “the” are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms “comprises” and/or “comprising,” when used in this specification, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof.
[0090] The corresponding structures, materials, acts, and equivalents of all means or step plus function elements in the claims below are intended to include any structure, material, or act for performing the function in combination with other claimed elements as specifically claimed. The description of the present invention has been presented for purposes of illustration and description, but is not intended to be exhaustive or limited to the invention in the form disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the invention. The embodiment was chosen and described in order to best explain the principles of the invention and the practical application, and to enable others of ordinary skill in the art to understand the invention for various embodiments with various modifications as are suited to the particular use contemplated.
[0091] It is to be understood that any feature described in relation to any one embodiment may be used alone, or in combination with other features described, and may also be used in combination with one or more features of any other of the embodiments, or any combination of any other of the embodiments. The invention is not limited to the embodiments described above, which may be varied within the scope of the accompanying claims. For example, different coating and/or printing techniques may be used to apply a polysilane layer onto a substrate. Exemplary printing techniques that may be used with the invention include gravure printing, screen printing, flexographic/letterpress printing and/or offset printing. Similarly, exemplary coating techniques that may be used include slot die coating, roller coating, dip coating, air knife coating, etc. Further, other (flexible) substrates than plastic substrates may be used as a support substrate including metallic, fibre-type (woven or non-woven) sheets, etc.