The described subject matter relates to transparent conducting oxides and production thereof.
Transparent conducting oxide (TCO) coatings may be applied to substrates or over-coated on top of other previously deposited layers. Such layers may exhibit high transparency with electrical conductivity ranging from semiconducting to highly conducting. Accordingly, these coatings, or “thin films” as they are often referred to, may be used for a wide range of opto-electronic applications. For example, thin films may be used in the manufacture of electronic devices, such as, liquid crystal displays (LCDs), and touch panel devices (e.g., personal digital assistants (PDAs) and electronic controllers), photovoltaic solar cells and transparent thin film transistors to name only a few examples.
Known deposition techniques may be implemented during the manufacture process to deposit a metal oxide as the thin film on a substrate. Indium Tin Oxide (also commonly referred to as ITO) is often used because it can be deposited at low temperatures, results in smooth films, can be readily etched, and exhibits thermal stability. However, other amorphous or polycrystalline metal oxides may also be used depending on the desired properties of the thin film, cost, operational parameters, and other factors. Furthermore, vacuum deposition using sputtering is a large area process that is widely used in the coating industry.
Achieving the desired opto-electronic properties of the thin film is typically dependent on the amount of oxygen introduced during the deposition process. Unfortunately, controlling the amount of oxygen (or its partial pressure) can be very difficult, especially in large-area production sputtering systems. For example, the amount of oxygen from the target changes with target use. Oxygen from the substrate and internal surfaces of the vacuum chamber is subject to seasonal/daily humidity variations. Maintenance activities also alter outgassing of internal surfaces. In addition, there can also be air leaks in the system. Accordingly, optimizing TCO film properties by controlling the oxygen partial pressure is a delicate process, and ensuring film reproducibility is time consuming and expensive.
The foregoing examples of the related art and limitations related therewith are intended to be illustrative and not exclusive. Other limitations of the related art will become apparent to those of skill in the art upon a reading of the specification and a study of the drawings.
The following embodiments and aspects thereof are described and illustrated in conjunction with systems, tools and methods that are meant to be exemplary and illustrative, not limiting in scope. In various embodiments, one or more of the above-described problems have been reduced or eliminated, while other embodiments are directed to other improvements.
An exemplary method of producing a transparent conducting oxide (TCO) material may comprise: providing a TCO target containing a high-permittivity oxide in a vacuum deposition chamber, and depositing a metal oxide on a substrate from a target in the process chamber to form a thin film having enhanced optical properties without substantially decreasing electrical quality In this example, the thin film has a high infrared transparency.
Another exemplary method of producing a transparent conducting oxide (TCO) material may comprise: providing a TCO target containing a material that yields a lower-permittivity oxide placing the target into a process chamber, and depositing a metal oxide on a substrate from a target in the process chamber to form a thin film having enhanced optical properties without substantially decreasing electrical quality. In this example, the thin film has a lower infrared transparency.
An exemplary method of optimizing electrical and optical properties of a TCO thin film may comprise: providing a TCO target containing a material that widens the range of oxygen partial pressures needed during deposition, and depositing a metal oxide film on a substrate from a target in the process chamber to form the TCO thin film.
Exemplary TCO thin films produced according to the methods described herein may exhibit desirable properties such as high electrical conductivity, high (or low) transparency, and/or other desirable opto-electronic properties.
In addition to the exemplary aspects and embodiments described above, further aspects and embodiments will become apparent by reference to the drawings and by study of the following descriptions.
Exemplary embodiments are illustrated in referenced figures of the drawings. It is intended that the embodiments and figures disclosed herein are to be considered illustrative rather than limiting.
Briefly, a sputter deposition process to make transparent conducting oxides (TCOs) may be implemented using either a metallic target in an oxygen atmosphere or a ceramic metal oxide target in an atmosphere which may or may not contain oxygen. Electrical and/or optical properties of the transparent conducting oxides may be controlled by varying the ratio of metals and/or the oxygen (e.g., wt %, stoichiometry, partial pressure, etc.) during the sputter deposition process. Accordingly, the transparent conducting oxides produced according to the methods disclosed herein have application in a wide variety of opto-electronic devices. Exemplary transparent conducting oxides and methods of production thereof may be better understood with reference to the Figures and following discussion.
In an exemplary embodiment, the deposition process may be implemented as radio-frequency (RF) magnetron sputtering. A process chamber 100 is provided with a ceramic metal oxide alloy referred to as the target 110. The target 110 may include one or more metal species 112 (e.g., Cu, In, Zn, Ga, Cd, Sn, Al, Ti, and Sb, etc., including others that will be apparent to those skilled in the art). For purposes of illustration, the target 110 in
It is noted that metal and/or metal alloy targets may be used in place of metal oxide targets. It is also noted that direct current (DC) sputtering or pulsed DC sputtering may also be used instead of RF sputtering. It is also noted that the metal or metal-oxide target may be bombarded by ions from a separate ion source.
During the deposition process, the target 110 may be bombarded by ions 120 (e.g., Argon 40), which causes constituent atoms 130 (e.g., In, Sn, and oxygen ions) to be ejected from the surface of the target 110. These constituent atoms traverse the distance between the target and substrate and recombine to form metal oxide films on the substrate.
In exemplary embodiments, the substrate material 160 may be an electrically conducting and/or transparent material, e.g., glass, tin oxide-coated glass, copper, aluminum or other material. However, the substrate material 160 is not limited to any particular type of material. The substrate material 160 will depend at least to some extent on the application, as will be understood by those having ordinary skill in the art after becoming familiar with the teachings herein. The metal oxide coating may also be over-coated on previously deposited and processed layers on the substrate, such as, e.g., when making a top contact to a opto-electronic device with a layered structure.
It is noted that the deposition process may also include additional operations. In an exemplary embodiment, the substrate material 160 having the deposited metal oxide thin film 170 may be thermally annealed. Other operations may also include varying operating parameters, e.g., temperature, relative concentrations of the metal ions, etc. Still other operations may also be implemented, as may be required to produce composite materials with the desired physical and electronic properties.
Before continuing, it is also noted that the deposition process described above with reference to
Optimization of the properties of transparent conducting oxides involves maximizing their optical transmittance and electrical conductivity. Generally, these two characteristics are conflicting. That is, increasing either one usually means decreasing the other. Various figures-of-merit describing the performance of transparent conducting oxides have been used but a useful definition is given by equation (1), where A is the optical absorbance and Rw is the sheet resistance (Ω per square).
φ=log A/Rw, Equation (1)
The optical absorbance is generally expressed by Beer's law, in which α is the optical absorption coefficient (cm−1) and t is the thickness (cm).
A=exp(−αt), Equation (2)
Substitution of equation (2) in equation (1), and knowing that R0=ρ/t, gives equation (3), where σ is the conductivity (i.e., the reciprocal of the resistivity, ρ), and the dimensions of φ are ohms−1.
φ=σ/α. Equation (3)
Unlike other figures-of-merit, this quantity is independent of film thickness and depends only on fundamental properties of the material. Increasing the figure-of-merit may be achieved by an increase in conductivity, without an equal increase in optical absorption, or by a decrease in optical absorption, without an equivalent decrease in conductivity.
The absorption coefficient may be expressed in terms of the extinction coefficient, k, with λ being the wavelength.
Now from Maxwell's theory of electromagnetic radiation, the imaginary part of the dielectric permittivity is given by equation 5, where N is the refractive index.
∈2=2Nk, Equation (5)
In addition, Drude's theory of free electrons gives equation 6, where n is the free-carrier concentration (m−3), e is the electronic charge (coulombs), ∈0 is the permittivity of free space (farads m−1), ω is the angular frequency of the radiation (s−1) and τ is the relaxation time (s).
Hence, an alternative expression for the extinction coefficient is derived in equation (7).
Substituting equation (7) into equation (3) results in equation 8.
In addition, equation (9) can be substituted into equation (8) to give equation 10.
This expression may now be substituted into equation (2) and, knowing that σ=neμ, equation (11) may be derived, which reveals the significance of the relaxation time, τ.
φ=Nc∈0τ2ω2, Equation (11)
Equation 12 is from Maxwell's theory, where ∈1 is the real part of the dielectric permittivity, which is dimensionless.
∈1=N2−k2. Equation (12)
For most of the visible spectrum, k˜0 so N=√{square root over (∈1)}. Therefore, substituting the latter expression into equation (11) results in equation (13).
φ=√{square root over (∈1)}c∈0τ2ω2. Equation (13)
This shows that the figure-of-merit increases with the square root of the real part of the dielectric permittivity. This is true irrespective of the magnitudes of N and k. Hence, an increase in the permittivity of a TCO leads to an increase in its figure-of-merit for a given relaxation time. Although τ is a more sensitive factor (i.e., the figure-of-merit increases as its square), the influence of the permittivity has not generally been appreciated. However, this dependence helps to explain the results obtained with ZrO2 added to indium oxide. That is, the zirconia has a very large permittivity and, even in relatively small concentrations, may make a significant difference to the optical properties.
A method for producing TCO films may comprise: adding small amounts of oxides that have large values of high-frequency dielectric permittivity, ∈∞ (TiO2, ZrO2, HfO2, V2O5 etc.) to traditional TCO materials (e.g., In2O3:Sn, SnO2:F, ZnO:Al, etc). Such an embodiment improves the optical transmission of the resulting TCO film without reducing the electrical quality of the film.
In this method, the optical absorption of a TCO film is not only a function of its oxygen content (as discussed above) but also of its high-frequency dielectric permittivity (e). Using these formalisms, the effect can be mathematically modeled by systematically varying ∈∞ from a value of 4 to a value of 7 and observing the effect this has on the optical performance of a typical TCO. This range of ∈∞ is consistent with expected variations in the TCO films.
The following modeling shows the variation of the optical properties of films with typical carrier concentration, mobility and film thickness for TCOs.
The peak of the absorption vs. wavelength curves occurs close to the plasma wavelength. As the real part of the permittivity is increased, it may be seen that the peak of the absorption moves to a longer wavelength. Consequently, the optical absorption is reduced on the short-wavelength side of the plasma wavelength, which is desired for applications in the visible spectrum.
Accordingly, the method described above may be implemented to produce high quality sputtered In2O3:Zr films in pure Ar. Adding ZrO2 to the target of traditional TCOs improves film transparency in the visible range of wavelengths. Adding ZrO2 to the target of traditional TCOs also maintains high carrier concentration at higher oxygen partial pressures. The method may also be used to widen the process window during TCO production. It is noted that other refractory metals or metal oxides (e.g., In2O3:Hf) and/or other TCO host materials may also be used.
It is readily appreciated that applications of this technology may include, but are not limited to, liquid crystal displays (LCDs), touch panel devices (e.g., personal digital assistants or PDAs), photovoltaic solar cells, transparent thin film transistors, low-emissivity window glass, and other opto-electronic applications.
By way of example, the development of multi-junction thin-film photovoltaic solar cell devices with 25% conversion efficiency may be accomplished by incorporating the TCO materials produced according to the methods described herein into photovoltaic devices that have much higher NIR transmission than found in traditional TCOs. Specifically, TCOs may be used having both a low sheet resistance and a high transmission between about 800 and 1300 nm.
The increased transmittance of the TCO materials produced according to the methods described herein may also enable lower power consumption in flat panel displays (and hence a longer battery lifetime). The TCOs may also exhibit enhanced wear-resistance, mechanical durability, and/or chemical resistance.
In this example, thin films were fabricated of a traditional TCO material containing a small amount of a high-permittivity oxide. The goal was to gain an advantage in the optical properties from the high-∈ material without suffering loss of electrical quality. Films were produced by radio-frequency (RF) magnetron sputtering. Film composition was fixed by using sputtering targets that were custom fabricated using a small amount of ZrO2 for the high-∈ component, and In2O3 combined with SnO2 (ITO) for the traditional (host) TCO component.
A 2-inch diameter sputtering target was produced by a commercial manufacturer using 1 weight percent (wt %) of fully oxidized zirconium oxide (ZrO2) powder, 9 wt % of fully oxidized SnO2 powder, and 90 wt % fully oxidized In2O3 powder. The mixture was hot pressed to the approximate target dimensions required, followed by mechanically sizing to more-accurate dimensions. The target was then fully re-oxidized using a high-temperature anneal in ambient oxygen.
Film deposition was conducted in a high-vacuum sputtering system that allows for control of an ambient environment containing both Ar and oxygen. Films were deposited onto Corning 1737 glass substrates at temperatures of 350° C. The RF sputtered films produced using the ITO/ZrO2 target are referred to as “ITZO” films.
The example also included fabrication of RF sputter deposited ITO films. The ITO sputtering target was produced as described above, except that it did not contain ZrO2 (i.e., the mixture was 9 weight percent SnO2 and 91 wt % In2O3). The ITO films were produced during the same time period so that the films could be used as “control samples” to isolate effects due to the high-∈ component, (ZrO2), ITO. It should also be noted that the ITO films produced for this comparison are among the highest quality ITO films produced, and so a favorable comparison with these particular ITO films represents a very high standard.
In
It is readily observed in
It is noted that, although ZrO2 and ITO were used in this example, similar high-∈ oxides (e.g., TiO2, HfO2, etc.) and/or other traditional host TCO materials (SnO2:F, ZnO:Al, etc.) may also be used to produce similar results. It is also noted that the optical properties may be tuned to longer or to shorter wavelengths using the permittivity as a control parameter. In addition, the work function of the host TCO may be changed by the addition of high-∈ oxides, because these also tend to have a large work function.
At low levels of ambient oxygen, addition of Zr (or similar materials) to the In2O3 matrix (or similar TCOs) may limit the formation of low-transparency phases when the sputtering ambient environment cannot supply sufficient oxygen. But because Zr is also an effective donor in In2O3, both electrical and optical quality are maintained at low oxygen partial pressure.
At high levels of ambient oxygen, addition of Zr (or similar materials) to the In2O3 matrix may getter excess oxygen into strong ZrO2 bonding, allowing oxygen vacancies to be retained as donors and/or limiting detrimental effects of interstitial oxygen in the In2O3 lattice to be retained as donors. This may be similar to the gettering process in non-evaporative getter (NEG) materials where Zr is also used because of its high reactivity.
Both of these results can provide advantages in a TCO production environment because the range of oxygen partial pressure where optimum films are produced is extended, and because optimization is enabled by the target composition rather than the (less predictable) oxygen partial pressure in the sputtering ambient.
The Example discussed above is provided for purposes of illustration and is not intended to be limiting. Still other embodiments and modifications are also contemplated.
While a number of exemplary aspects and embodiments have been discussed above, those of skill in the art will recognize certain modifications, permutations, additions and sub combinations thereof. It is therefore intended that the following appended claims and claims hereafter introduced are interpreted to include all such modifications, permutations, additions and sub-combinations as arc within their true spirit and scope.
This application claims the benefit of U.S. patent application Ser. No. 11/718,628, filed on May 4, 2007 as a continuation-in-part application.
The United States Government has rights in this invention under Contract No. DE-AC36-99GO10337 between the United States Department of Energy and the National Renewable Energy Laboratory, a Division of the Midwest Research Institute.
Number | Name | Date | Kind |
---|---|---|---|
4395467 | Vossen, Jr. et al. | Jul 1983 | A |
5909623 | Saihara | Jun 1999 | A |
5922142 | Wu | Jul 1999 | A |
6042752 | Mitsui | Mar 2000 | A |
6137048 | Wu | Oct 2000 | A |
6169246 | Wu | Jan 2001 | B1 |
6180870 | Sano et al. | Jan 2001 | B1 |
6221495 | Wu | Apr 2001 | B1 |
6246071 | Qadri et al. | Jun 2001 | B1 |
6281035 | Gessert | Aug 2001 | B1 |
6569548 | Yamamoto et al. | May 2003 | B2 |
6606333 | Kadota | Aug 2003 | B2 |
6677063 | Finley | Jan 2004 | B2 |
6685623 | Presthus et al. | Feb 2004 | B2 |
6733895 | Kadota et al. | May 2004 | B2 |
6787253 | Iwabuchi et al. | Sep 2004 | B2 |
6852623 | Park et al. | Feb 2005 | B2 |
6908782 | Yan | Jun 2005 | B2 |
6936761 | Pichler | Aug 2005 | B2 |
7071121 | Punsalan et al. | Jul 2006 | B2 |
7186465 | Bright | Mar 2007 | B2 |
7699965 | Ikisawa et al. | Apr 2010 | B2 |
7727910 | Ahn et al. | Jun 2010 | B2 |
20020036286 | Ho et al. | Mar 2002 | A1 |
20030218153 | Abe | Nov 2003 | A1 |
20050062134 | Ho et al. | Mar 2005 | A1 |
20060118406 | Delahoy | Jun 2006 | A1 |
20070007125 | Krasnov | Jan 2007 | A1 |
20070116986 | Garg et al. | May 2007 | A1 |
20080118777 | Li et al. | May 2008 | A1 |
20080296569 | Ho et al. | Dec 2008 | A1 |
20090197757 | Fukushima | Aug 2009 | A1 |
20090297886 | Gessert et al. | Dec 2009 | A1 |
20100171082 | Gessert et al. | Jul 2010 | A1 |
20100288487 | Turley et al. | Nov 2010 | A1 |
20110084239 | Gessert et al. | Apr 2011 | A1 |
20110197958 | Li et al. | Aug 2011 | A1 |
20120097222 | Gessert et al. | Apr 2012 | A1 |
Number | Date | Country |
---|---|---|
1010377595 | Sep 2007 | CN |
2009116990 | Sep 2009 | WO |
Entry |
---|
PCT/US2007/060553 International Search Report Patent Family Members. |
Coutts et al., “Characterization of Transparent Conducting Oxides”, MRS Bulletin, 25, pp. 58-65 (Aug. 2000). |
Gessert, “Progress and Roadmap Alignment Company or Organization: National Center for Photovitaics [sic.] Funding Opportunity: EE&RE”, presented at the Solar Energy Technologies Program (SETP) Annual Program Review Meeting held Aug. 22-24, 2008 in Austin, Texas. |
Gessert et al., “High-Transparency Sputtered In2O3 and ITO Films Containing Zirconium”, presented at the AVS 54th International Symposium & Exhibition held Oct. 14-17, 2007 in Seattle, Washington. |
Burst et al., “RF-Sputtered ITO and ITO:Zr Studied by In Situ Spectroscopic Ellipsometry”, Photovoltaic Specialist Conference, 35th IEEE, Jun. 20-25, 2010. |
Calnan et al., “High mobility transparent conducting oxides for thin film solar cells”, Thin Solid Films, vol. 518, Issue 7, Jan. 31, 2010, pp. 1839-1849. |
Burst et al., “Recent Developments in Transparent Conducting Oxides for Thin-Film Solar Cells” (Abstract), AVS 57th International Symposium & Exhibition held Oct. 17-22, 2010 in Albuquerque, New Mexico. |
Miyata, et al., “New transparent conducting thin films using multicomponent oxides composed of ZnO and V2O5 prepared by magnetron sputtering”, Thin Solid Films, vol. 411, Issue 1, May 22, 2002, pp. 76-81. |
Tamura et al., “Donor-acceptor pair luminescence in nitrogen-doped ZnO films grown on lattice-matched ScAlMgO4 (0001) substrates”, Solid State Communications, vol. 127, Issue 4, Jul. 2003, pp. 265-269. |
Kaminska et al., “Properties of p-Type ZnO Grown by Oxidation of Zn-Group-V Compounds”, Mater. Res. Soc. Symp. Proc. vol. 957, Fall 206, pp. 121-126. |
Wang et al., “Growth of p-type ZnO thin films by (N, Ga) co-doping using DMHy dopant”, J. Phys. D: Appl. Phys. vol. 40, No. 15, Aug. 7, 2007, pp. 4682-4685. |
Tompa et al., “A comparative study of MOCVD produced Zno films doped with N, As, P and Sb”, Mater. Res. Soc. Symp. Proc., vol. 957, Fall 2007, pp. 283-287. |
Exharhos et al., “Discovery-based design of transparent conducting oxide films”, Thin Solid Films, vol. 515, Issue 18, Jun. 25, 2007, pp. 7025-7052. |
U.S. Appl. No. 11/718,628 USPTO Restriction Requirement dated Feb. 25, 2011. |
U.S. Appl. No. 11/718,628 USPTO Non-Final Office Action dated Apr. 1, 2011. |
U.S. Appl. No. 11/718,628 USPTO Final Rejection dated Sep. 19, 2011. |
U.S. Appl. No. 11/718,628 USPTO Non-Final Office Action dated Sep. 11, 2013. |
PCT/US07/60553 International Search Report and Written Opinion dated Oct. 10, 2007. |
PCT/US07/60553 International Preliminary Report on Patentability dated Jul. 21, 2009. |
Haacke, “Transparent Conduction Coatings,” Annual Review of Materials Science, vol. 7, Aug. 1997, pp. 73-93. |
Chopra et al., “Transparent Conductor—A Status Review,” Thin Solid Films, vol. 102, Issue 1, Apr. 1983, pp. 1-46. |
Kanai, “Electrical Properties of In2O3 Singe Crystals Doped with Metallic Donor Impurity,” Japan Journal of Applied Physics, vol. 23, No. 1, Jan. 1984, p. 127. |
Yoshida et al., “Thin-Film Indium Oxide Doped with Refractory Metals,” MRS Symp. Proc. vol. 747, pp. V1.4.1-V1.4.6, 2003. |
Gessert et al., “Summary Abstract: The dependence of the electrical properties of ion-beam supttered indium tin oxide on its composition and structure,” J. Vac. Sci. Technol. A. vol. 5, No. 4, Jul./Aug. 1987. |
Kostlin, “Electrical Properites and Defect Model of Tin-Doped Indium Oxide Layers,” Applied Physics A, vol. 27, Issue 4, Apr. 1982, pp. 197-206. |
Ohta et al., “Highly electrically conductive indium-tin-oxide thin films epitaxially grown on yittria-stabilized zirconia (100) by pulsed-laser deposition,” Applied Physics Letters, vol. 76, No. 19, May 8, 2000, pp. 2740-2742. |
Ohta et al., “Surface morphology and crystal quality of low resistive indium tin oxide grown on yittria-stabilized zirconia,” Journal of Applied Physics, vol. 91, No. 6, Mar. 15, 2002, pp. 3547-3550. |
Gessert et al., “Advantages of transparent conducting oxide thin films with controlled pemlitivity for thin film photovoltaic solar cells,” Thin Solid Films, vol. 519, Issue 21, Aug. 31, 2011, pp. 7146-7148. |
Number | Date | Country | |
---|---|---|---|
20090297886 A1 | Dec 2009 | US |
Number | Date | Country | |
---|---|---|---|
Parent | 11718628 | US | |
Child | 12130788 | US |