Compositions and methods for semiconductor processing and devices formed therefrom
09793188 · 2017-10-17
Inventors
Cpc classification
H01L2924/0002
ELECTRICITY
Y02E10/50
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
H01L23/3171
ELECTRICITY
H01L2924/0002
ELECTRICITY
H01L2924/00
ELECTRICITY
International classification
Abstract
The present invention relates generally to the field of semiconductor devices, including solar cells, and compositions and methods for processing semiconductor devices, passivation of semiconductor surfaces, semiconductor etching and anti-reflective coatings for semiconductor devices.
Claims
1. A method of growing an oxide layer on a semiconductor device, the method comprising the step of contacting at least one surface of a semiconductor device with the dilute aqueous solution comprising: (a) an oxidant, wherein the oxidant is H.sub.2SeO.sub.3; (b) a compound comprising fluorine; (c) one or more additives; and (d) water.
2. The method of claim 1, wherein the composition comprises A weight percent the oxidant, B weight percent of the compound comprising fluorine, C weight percent of the one or more additives, and D weight percent water, wherein the sum of A, B, C, and D is about 100.
3. The method of claim 2, wherein A is from about 0.01 weight percent to about 1 weight percent.
4. The method of claim 2, wherein B is from about 0.1 weight percent to about 10 weight percent.
5. The method of claim 2, wherein C is from about 1 weight percent to about 50 weight percent.
6. The method of claim 2, wherein the ratio of B to C is from about 4:1 to about 1:20.
7. The method of claim 1, wherein the compound comprising fluorine comprises one or more of HF, H.sub.2SiF.sub.6, NH.sub.4F, H.sub.2TiF.sub.6, BaF, BF.sub.4, NaF, metal fluorides and non-metal fluorides.
8. The method of claim 1, wherein the one or more additives comprise one or more of HF, HCl, HBr, HI, H.sub.3PO.sub.4, and NH.sub.4OH.
9. The method of claim 1, wherein the oxidant is H.sub.2SeO.sub.3 which is present in an amount of from about 0.01 g/L to about 1 g/L.
10. A method of growing an oxide layer on a semiconductor device, the method comprising the step of contacting at least one surface of a semiconductor device with the dilute aqueous solution comprising: (a) an oxidant; (b) a compound comprising fluorine; (c) one or more additives; and (d) water, wherein the oxidant comprises one or more of fluorine, chlorine, or bromine.
11. The method of claim 10, wherein the oxidant is selected from chloric acid and bromic acid.
12. A semiconductor device comprising at least one passivation oxide layer, wherein the passivation oxide layer is formed by treating the semiconductor device with the composition of claim 1, wherein the passivation oxide layer has thickness of from about 40 Å to about 200 Å.
13. The semiconductor device of claim 12, wherein the semiconductor device exhibits a sheet rho after forming the passivation oxide layer of from about 50 to about 120 ohm/sq.
14. The semiconductor device of claim 12, wherein the semiconductor device exhibits a sheet rho delta after forming the passivation oxide layer of from about 3 to about 20 ohm/sq.
15. A semiconductor device comprising at least one passivation oxide layer, wherein the passivation oxide layer is formed by treating the semiconductor device with the composition of claim 10, wherein the passivation oxide layer has thickness of from about 40 Å to about 200 Å.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) The skilled artisan will understand that the drawings primarily are for illustrative purposes and are not intended to limit the scope of the inventive subject matter described herein. The drawings are not necessarily to scale; in some instances, various aspects of the inventive subject matter disclosed herein may be shown exaggerated or enlarged in the drawings to facilitate an understanding of different features. In the drawings, like reference characters generally refer to like features (e.g., functionally similar and/or structurally similar elements).
(2)
(3)
(4)
(5)
(6)
(7)
(8)
(9)
DETAILED DESCRIPTION
(10) The present invention discloses provides compositions for treating the semiconductor devices to obtain certain desired properties. For example, in etching silicon (Si) wafers to obtain a certain surface texture, a composition comprising an oxidant, and an acid or base to remove the oxidized surface may be used. In some embodiments, the composition may also include a buffering agent and/or a diluent. The buffering agent may be used to control the acidity of the composition and further replenish ions that are used up in the etching process, thereby contributing to the maintenance of a stable etching rate. The diluent may be used to transport out products of the surface treatment process and other excess reactants. The performance of the composition may be measured by, for example, the change in the sheet resistance rho (Δρ) of the surface of the semiconductor device being treated by the composition.
(11)
Si+4HIO.sub.3.fwdarw.SiO.sub.2+4IO.sub.2+2H.sub.2O.
(12) The efficiency of the above chemical reaction depends on the acidity of the composition and/or the concentration of iodic acid in the composition. For example, iodic acid is a stronger oxidant in an acidic solution as opposed to a basic one. In some embodiments, hydrocholoric acid (HCl) may be used to regulate the pH level of the composition. The oxidizing ability of the composition may also depend on how strongly iodic acid dissociates in a solution, a property that can be quantitatively measured by the acid dissociation constant K.sub.a, or more commonly by the logarithm of the acid dissociation constant pK.sub.a. The pK.sub.a of iodic acid (i.e., half the amount of the iodic acid has dissociated into the conjugate base IO.sub.3.sup.− and hydrogen ions H.sup.+) is 0.75, indicating an acid that dissociates strongly and may not be as effective of an oxidant in a composition with a higher pH value. For example, as shown in
(13) In the exemplary embodiments shown in
SiO.sub.2+HF.fwdarw.H.sub.2SiF.sub.6+2H.sub.2O.
(14) In some embodiments, additional additives (e.g., non-oxidizing acids or bases) may be included in the composition used to treat the wafer surface. For example, ammonium fluoride (NH.sub.4F) may be used as a buffering agent to control the pH of the composition and serve as source of additional fluoride ions. In addition, diluents such as acetic acid and/or water may be used as medium to transport reactants/by-products out of the silicon surface. This results in a more stable and controllable etching rate.
(15)
(16) In some embodiments, it may be desirous to use other types of acids in etching compositions instead of, or in conjunction with, HCl. Examples of other acids that may be used in an etching composition are sulfuric acid (H.sub.2SO.sub.4), nitric acid, or other mineral acids. The effect of some of the acids on the growth of oxide layers on semiconductor surfaces may depend on the concentration of the oxidant in the composition. For example,
(17) In contrast, in some embodiments, the effect of adding nitric acid in an etching composition for treating semiconductor surfaces remains qualitatively similar for concentrations of the oxidant HIO.sub.3. For example, the change in the sheet resistances Δρ 322, 342 and 362 of a semiconductor device treated with a compositions comprising HIO.sub.3, when the composition comprises little or no HNO.sub.3, are lower than Δρ 312, 332 and 352, respectively, for about same levels of HIO.sub.3 concentration in compositions comprising nitric acid.
(18)
(19) Applicants have appreciated that some of the components of the composition utilized in treating surfaces of semiconductor devices such as but not limited to silicon may not be desirable for various reasons. For example, HF is known for being a very dangerous material. It is capable of penetrating skin and attacking flesh and bones even in its diluted form, while a victim may not feel any indication until it is too late due to HF's weak acidity in the dilute state. Similarly, it may be desirable to use other acids in the compositions instead of, or perhaps along with, HCl. For example, one may wish to control the acidity of the compositions (for example, change the pH level) for different reasons. For example, some oxidants, such as but not limited to iodic acid, are better oxidants in an acidic environment, and keeping the acidity of the composition from deteriorating (i.e., keeping the pH level low) may help with preventing the degradation of the oxidants' performance when treating semiconductor devices. Applicants have appreciated the need to accommodate these priorities, and have discovered components for compositions to treat semiconductor surfaces whose performances are not degraded when the pH level is increased, and result in oxide film growth on the surfaces.
(20)
(21) In some embodiments, the composition used to treat semiconductor surfaces may comprise different proportions of oxidants, compounds, additives, and diluent (e.g., water). For example, the composition may comprise A wt % of an oxidant, B wt % of a compound comprising fluorine, C wt % of one or more additives, and D wt % water, wherein the sum of A, B, C, and D is about 100. In some embodiments, A ranges from about 0.01 to about 1; B ranges from about 0.1 to about 10, C ranges from about 1 to about 50, etc. As such, for example, in some embodiments, the ratio of B to C may range from about 4:1 to about 1:20. The oxidants in the composition may include one or more of halogens (e.g., fluorine, chlorine, bromine, iodine, astatine) and/or chalcogens (e.g., oxygen, sulfur, selenium, tellurium, polonium). For example, the oxidant in the composition may be selenous acid, and in such embodiments, selenous acid may be present in the composition in an amount ranging from about 0.01 g/L to about 1 g/L. As another example, the oxidant comprising one or more of halogens may be chloric acid or bromic acid. In some embodiments, the oxidants may be oxyacids (i.e., oxygen containing acids), exemplary embodiments of which have the empirical chemical formula H.sub.aR.sub.bO.sub.c. In such embodiments, a in the chemical formula may assume the values 1, 2, 3 or 4; b may assume 1, 2 or 3; and c may assume the values 1, 2, 3, 4, 5, 6, 7 or 8. In other embodiments, the oxyacid may have chemical formula of HRO.sub.3 or H.sub.2RO.sub.3. In these embodiments, i.e., in the embodiments where the oxyacid has one of the chemical formulae H.sub.aR.sub.bO.sub.c, HRO.sub.3 and H.sub.2RO.sub.3, R may comprise a halogen or a chalcogen. In some embodiments, the oxyacid may have a trigonal pyramidal molecular geometry. In some embodiments, one may form a dilute aqueous solution comprising water and any of the embodiments of the compositions disclosed herein. In such embodiments, the ratio of composition to water may be from about 1:4 to about 1:10.
(22) In some embodiments, the compound included in the composition to treat semiconductor surfaces may comprise fluorine. Examples of such compounds are HF and NH.sub.4F. In some embodiments, the compound comprising fluorine may comprise one or more of HF, hydrofluosilicic acid (H.sub.2SiF.sub.6), NH.sub.4F, fluorotitanic acid (H.sub.2TiF.sub.6), barium fluoride (BaF), barium ferrite (BF.sub.4), sodium fluoride (NaF), metal fluorides and non-metal fluorides. In some embodiments, the additives included in the composition to treat semiconductor surfaces may comprise ammonium hydroxide, HF, HCl, Hydrogen bromide (HBr), Hydrogen Iodide (HI), phosphoric acid (H.sub.3PO.sub.4) and ammonium hydroxide.
(23) In some embodiments, the compositions described in the present invention may be used to treat surfaces of semiconductor devices, an exemplary embodiment of a semiconductor material being silicon. In some embodiments, one may also use an aqueous solution comprising the compositions and water to treat the semiconductor devices. Such semiconductor devices, when treated by either the compositions or the aqueous solution comprising the composition, may have a passivated oxide layer formed on their surfaces. Such oxide layers may have a wide range of thicknesses, ranging from about 40 Å to about 200 Å. The growth of passivated oxide layer may contribute to surface resistance (sheet rho(ρ)) of the semiconductor device. For example, the contribution coming from being treated by a composition or an aqueous solution may increase the surface resistance by some amount, i.e., it may change the sheet rho by an amount Δρ. In some embodiments, the sheet rho delta Δρ may range from about 3 Ω/sq to about 20 Ω/sq. In some embodiments, the change Δρ may be about 9 to about 15 Ω/sq. And in yet some embodiments, sheet rho delta may be about 10 Ω/sq. Changes in the surface resistance of a semiconductor device as consequences of passivated oxide layers forming on its surfaces from being treated by compositions or aqueous solutions described herein may lead to an increase in the total sheet rho of the semiconductor device. For example, the sheet rho of such semiconductor devices may range from about 50 Ω/sq to about 120 Ω/sq. In some embodiments, the sheet rho may be from about 60 Ω/sq to about 90 Ω/sq. Another consequence of the growth of passivated oxide layers may be a red shift in the location of the wavelength at which reflectance minimum takes place. For example, a composition treated semiconductor device with a passivated layer may have a reflectance minimum at a wavelength greater than a substantially similar semiconductor device which may not comprise a passivated layer. As an example, the red shift of a light incident on a surface of a composition treated semiconductor with passivated layer may range from about 20 nm to about 45 nm.
(24) While various inventive embodiments have been described and illustrated herein, those of ordinary skill in the art will readily envision a variety of other means and/or structures for performing the function and/or obtaining the results and/or one or more of the advantages described herein, and each of such variations and/or modifications is deemed to be within the scope of the inventive embodiments described herein. More generally, those skilled in the art will readily appreciate that all parameters, dimensions, materials, and configurations described herein are meant to be exemplary and that the actual parameters, dimensions, materials, and/or configurations will depend upon the specific application or applications for which the inventive teachings is/are used. Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, many equivalents to the specific inventive embodiments described herein. It is, therefore, to be understood that the foregoing embodiments are presented by way of example only and that, within the scope of the appended claims and equivalents thereto, inventive embodiments may be practiced otherwise than as specifically described and claimed. Inventive embodiments of the present disclosure are directed to each individual feature, system, article, material, kit, and/or method described herein. In addition, any combination of two or more such features, systems, articles, materials, kits, and/or methods, if such features, systems, articles, materials, kits, and/or methods are not mutually inconsistent, is included within the inventive scope of the present disclosure.
(25) Also, various inventive concepts may be embodied as one or more methods, of which an example has been provided. The acts performed as part of the method may be ordered in any suitable way. Accordingly, embodiments may be constructed in which acts are performed in an order different than illustrated, which may include performing some acts simultaneously, even though shown as sequential acts in illustrative embodiments.
(26) All definitions, as defined and used herein, should be understood to control over dictionary definitions, definitions in documents incorporated by reference, and/or ordinary meanings of the defined terms.
(27) The indefinite articles “a” and “an,” as used herein in the specification and in the claims, unless clearly indicated to the contrary, should be understood to mean “at least one.”
(28) The phrase “and/or,” as used herein in the specification and in the claims, should be understood to mean “either or both” of the elements so conjoined, i.e., elements that are conjunctively present in some cases and disjunctively present in other cases. Multiple elements listed with “and/or” should be construed in the same fashion, i.e., “one or more” of the elements so conjoined. Other elements may optionally be present other than the elements specifically identified by the “and/or” clause, whether related or unrelated to those elements specifically identified. Thus, as a non-limiting example, a reference to “A and/or B”, when used in conjunction with open-ended language such as “comprising” can refer, in one embodiment, to A only (optionally including elements other than B); in another embodiment, to B only (optionally including elements other than A); in yet another embodiment, to both A and B (optionally including other elements); etc.
(29) As used herein in the specification and in the claims, “or” should be understood to have the same meaning as “and/or” as defined above. For example, when separating items in a list, “or” or “and/or” shall be interpreted as being inclusive, i.e., the inclusion of at least one, but also including more than one, of a number or list of elements, and, optionally, additional unlisted items. Only terms clearly indicated to the contrary, such as “only one of” or “exactly one of,” or, when used in the claims, “consisting of,” will refer to the inclusion of exactly one element of a number or list of elements. In general, the term “or” as used herein shall only be interpreted as indicating exclusive alternatives (i.e. “one or the other but not both”) when preceded by terms of exclusivity, such as “either,” “one of,” “only one of,” or “exactly one of.” “Consisting essentially of,” when used in the claims, shall have its ordinary meaning as used in the field of patent law.
(30) As used herein in the specification and in the claims, the phrase “at least one,” in reference to a list of one or more elements, should be understood to mean at least one element selected from any one or more of the elements in the list of elements, but not necessarily including at least one of each and every element specifically listed within the list of elements and not excluding any combinations of elements in the list of elements. This definition also allows that elements may optionally be present other than the elements specifically identified within the list of elements to which the phrase “at least one” refers, whether related or unrelated to those elements specifically identified. Thus, as a non-limiting example, “at least one of A and B” (or, equivalently, “at least one of A or B,” or, equivalently “at least one of A and/or B”) can refer, in one embodiment, to at least one, optionally including more than one, A, with no B present (and optionally including elements other than B); in another embodiment, to at least one, optionally including more than one, B, with no A present (and optionally including elements other than A); in yet another embodiment, to at least one, optionally including more than one, A, and at least one, optionally including more than one, B (and optionally including other elements); etc.
(31) In the claims, as well as in the specification above, all transitional phrases such as “comprising,” “including,” “carrying,” “having,” “containing,” “involving,” “holding,” “composed of,” and the like are to be understood to be open-ended, i.e., to mean including but not limited to. Only the transitional phrases “consisting of” and “consisting essentially of” shall be closed or semi-closed transitional phrases, respectively, as set forth in the United States Patent Office Manual of Patent Examining Procedures, Section 2111.03.