Plasmonic enhancement of zinc oxide light absorption for sunscreen applications

Abstract
Zinc oxide compositions as well as techniques for plasmonic enhancement of zinc oxide light absorption for sunscreen applications are provided herein. One example method includes selecting one or more metal particles to be used in conjunction with one or more zinc oxide particles in a sunscreen composition, wherein said selecting is based on the plasmon resonance frequency associated with each of the metal particles; and coating at least one portion of the surface of each of the one or more zinc oxide particles with the metal particles. Another example method includes selecting one or more metal particles to be used in conjunction with one or more zinc oxide particles in a sunscreen composition, wherein said selecting is based on the plasmon resonance frequency associated with each of the metal particles; and blending the metal particles and the zinc oxide particles within a medium to create the sunscreen composition.
Description
FIELD

The present application generally relates to chemical technology, and, more particularly, to sunscreen technologies.


BACKGROUND

Sunscreen creams and other such compositions are commonly used to prevent ultraviolet (UV) radiation (also referred to herein as “light” in this context) from reaching the skin of a human user and causing damage. It is noted that UV light is an electromagnetic radiation with a wavelength range between approximately 280 nanometers (nm) and approximately 400 nanometers (specifically, that is the range of UV radiation that is not absorbed by the ozone).


A common active ingredient of existing sunscreen compositions is zinc oxide (ZnO). ZnO is a semiconductor that has a specific band gap, and particles of ZnO used in existing sunscreen compositions are typically approximately 50-200 nm in size. Additionally, in existing sunscreen compositions, typical ZnO materials are capable of absorbing UV light (that is, blocking the UV light from passing through the sunscreen composition to be absorbed by the skin of the user) within a wavelength range of approximately 290 nm through only approximately 350-380 nm.


Additionally, high sun protection factor (SPF) sunscreen compositions, which can absorb a large majority of the UV light in the range of 290-380 nm, require the addition of a higher density of ZnO particles, which causes the composition to become white and/or opaque due to light scattering from the ZnO particles, and which is an often undesirable property to consumers.


SUMMARY

In one embodiment of the present invention, zinc oxide compositions, methods of fabrications thereof and methods of use thereof are provided. An exemplary method can include selecting one or more metal particles to be used in conjunction with one or more zinc oxide particles in a sunscreen composition, wherein said selecting is based on the plasmon resonance frequency associated with each of the metal particles. Such an exemplary method can also include coating at least one portion of the surface of each of the one or more zinc oxide particles with the one or more selected metal particles.


In another embodiment of the invention, a sunscreen composition can include multiple zinc oxide particles suspended within a medium, and one or more metal particles coated on at least one portion of the surface of each of the multiple zinc oxide particles, wherein each of the metal particles comprises a plasmon resonance frequency that supplements the light absorption capabilities of the multiple zinc oxide particles.


Additionally, in another embodiment of the invention, an exemplary method can include selecting one or more metal particles to be used in conjunction with one or more zinc oxide particles in a sunscreen composition, wherein said selecting is based on the plasmon resonance frequency associated with each of the metal particles; and blending the one or more selected metal particles and the one or more zinc oxide particles within a medium to create the sunscreen composition.


In yet another embodiment of the invention, a sunscreen composition can include multiple zinc oxide particles suspended within a medium; and one or more metal particles and the multiple zinc oxide particles blended within the medium, wherein each of the metal particles comprises a plasmon resonance frequency that supplements the light absorption capabilities of the multiple zinc oxide particles.


These and other objects, features and advantages of the present invention will become apparent from the following detailed description of illustrative embodiments thereof, which is to be read in connection with the accompanying drawings.





BRIEF DESCRIPTION OF THE DRAWINGS


FIG. 1 is a diagram illustrating a ZnO particle coated with multiple metal nanoparticles, according to an example embodiment of the invention;



FIG. 2 is a flow diagram illustrating techniques, according to an embodiment of the invention;



FIG. 3 is a flow diagram illustrating techniques, according to an embodiment of the invention.





DETAILED DESCRIPTION

As described herein, an embodiment of the present invention includes ZnO compositions as well as techniques for plasmonic enhancement of ZnO light absorption for sunscreen applications. As further detailed herein, one or more embodiments of the invention include generating ZnO compositions and methods of use thereof for effectively blocking more and/or all of the complete spectrum of UV light (that is, as noted above, the UV radiation that is not absorbed by the ozone, and which ranges between approximately 280 nm and 400 nm) while also preventing whitening effects caused by the scattering of light in the visible spectrum (that is, radiation between approximately 400 nm and 700 nm). As used herein, “scattering” refers to the deflection of rays of visible light from the rays' original path due to interaction with particle surfaces.


As further detailed herein, one or more embodiments of the invention include enhancing the light absorption of ZnO particles by using plasmon resonances. Such an embodiment of the invention can include coating at least one portion of the surface of a ZnO particle (of a sunscreen composition) with one or more metal particles (or nanoparticles) that exhibit plasmon resonances. Different metals have different resonance frequencies, and the metals used in connection with one or more embodiments of the invention can include, for example, silver (Ag) and gold (Au).


In one or more embodiments of the invention, the size of the metal particles used can dictate the resonant energy, wherein smaller particles have higher-energy resonances. Accordingly, in at least one embodiment of the invention, the size of the metal particles used can be less than 30 nm, such as, for example, between 5-10 nm.


As detailed herein, the metal particles themselves attenuate light at their respective resonant frequency. By incorporating the metal particles into the sunscreen formulation, the attenuation of light by ZnO is supplemented by the light attenuation of the plasmonic particles. Accordingly, in one or more embodiments of the invention, UV light is attenuated by the plasmonic metal nanoparticles.


By way merely of example, as the nanoparticle size of a metal such as silver decreases, the wavelength of the resonance blue-shifts. To enhance the absorption of a sunscreen composition/formulation at approximately 400 nm, at least one example embodiment of the invention can include using silver nanoparticles of approximately 10 nm in size.



FIG. 1 is a diagram illustrating a ZnO particle coated with multiple metal nanoparticles, according to an example embodiment of the invention. By way of illustration, FIG. 1 depicts metal nanoparticles 104-1 through 104-8 (collectively, 104) attached to and/or deposited upon a ZnO particle 102 within a sunscreen composition to enhance absorption of the ZnO particle 102 at a resonant frequency. By way of example, silver nanoparticles can be grown directly onto a ZnO particle, using the ZnO particle as a nucleation center. Additionally, in one or more embodiments of the invention, ZnO can be coated onto a metallic silver nanoparticle so as to encase the silver nanoparticle inside of a ZnO particle. One technique for carrying out such an embodiment can include solution approaches. Further, in yet another embodiment of the invention, plasmonic silver nanoparticles can be mixed and/or blended into the ZnO particle sunscreen composition.


As detailed herein, a coating as illustrated in the example embodiment of FIG. 1 can induce a surface plasmon resonance which supplements the light attenuation properties of the ZnO particle 102. Also, in at least one embodiment of the invention, the size of the metal particles/nanoparticles can be selected to create a resonance at a photon energy which is not adequately absorbed by ZnO, so as to complement the oxide's absorption properties. Further, the effect of the metal nanoparticles can be proportional to the number of nanoparticles used.



FIG. 2 is a flow diagram illustrating techniques, according to an embodiment of the present invention. Step 202 includes selecting one or more metal particles to be used in conjunction with one or more zinc oxide particles in a sunscreen composition, wherein said selecting is based on the plasmon resonance frequency associated with each of the metal particles. The metal particles can include one or more silver particles, one or more gold particles, or a combination of one or more silver particles and one or more gold particles.


Additionally, each of the one or more metal particles can be of a size of less than 30 nanometers. By way of example, in at least one embodiment of the invention, each of the one or more metal particles can be of a size of between five and ten nanometers. Further, in one or more embodiments of the invention, the metal particles can include a number of the metal particles selected based on a desired attenuation magnitude proportional to the number of the metal particles selected.


Step 204 includes coating at least one portion of the surface of each of the one or more zinc oxide particles with the one or more selected metal particles.


Also, an additional embodiment of the invention includes a sunscreen composition that includes multiple zinc oxide particles suspended within a medium, and one or more metal particles coated on at least one portion of the surface of each of the multiple zinc oxide particles, wherein each of the metal particles comprises a plasmon resonance frequency that supplements the light absorption capabilities of the multiple zinc oxide particles.



FIG. 3 is a flow diagram illustrating techniques, according to an embodiment of the present invention. Step 302 includes selecting one or more metal particles to be used in conjunction with one or more zinc oxide particles in a sunscreen composition, wherein said selecting is based on the plasmon resonance frequency associated with each of the metal particles. The metal particles can include one or more silver particles, one or more gold particles, or a combination of one or more silver particles and one or more gold particles.


Additionally, each of the one or more metal particles can be of a size of less than 30 nanometers. By way of example, in at least one embodiment of the invention, each of the one or more metal particles can be of a size of between five and ten nanometers. Further, in one or more embodiments of the invention, the metal particles can include a number of the metal particles selected based on a desired attenuation magnitude proportional to the number of the metal particles selected.


Step 304 includes blending the one or more selected metal particles and the one or more zinc oxide particles within a medium to create the sunscreen composition.


Also, an additional embodiment of the invention includes a sunscreen composition that includes multiple zinc oxide particles suspended within a medium, and one or more metal particles and the multiple zinc oxide particles blended within the medium, wherein each of the metal particles comprises a plasmon resonance frequency that supplements the light absorption capabilities of the multiple zinc oxide particles.


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, steps, operations, elements, and/or components, but do not preclude the presence or addition of another feature, step, operation, element, component, and/or group thereof.


At least one embodiment of the present invention may provide a beneficial effect such as, for example, coating a ZnO particle with one or more metal particles to create a resonance at a photon energy that is not efficiently absorbed by the ZnO particle.


The descriptions of the various embodiments of the present invention have been presented for purposes of illustration, but are not intended to be exhaustive or limited to the embodiments 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 described embodiments. The terminology used herein was chosen to best explain the principles of the embodiments, the practical application or technical improvement over technologies found in the marketplace, or to enable others of ordinary skill in the art to understand the embodiments disclosed herein.

Claims
  • 1. A sunscreen composition for human use consisting of: a core zinc oxide particle suspended within a medium, wherein the zinc oxide particle is 50-200 nanometers in size; and(i) multiple silver particles, each encased in a zinc oxide particle, (ii) one or more silver nanoparticles, and (iii) multiple gold particles, all positioned on a portion of the surface of the core zinc oxide particle, wherein the portion is less than the entirety of the surface of the core zinc oxide particle, and wherein each of the encased silver particles, each of the one of more silver nanoparticles, and each of the multiple gold particles is a size of between five and ten nanometers.
  • 2. A method of creating a sunscreen composition for human use, consisting of: encasing each of multiple silver particles inside a zinc oxide particle by coating the surface of each of the silver particles with zinc oxide, wherein each of the silver particles is a size of between five and ten nanometers; andcovering a portion of the surface of a core zinc oxide particle with (i) the encased silver particles, (ii) one or more silver nanoparticles, and (iii) multiple gold particles by depositing (i) the encased silver particles, (ii) the one or more silver nanoparticles, and (iii) the multiple gold particles on the surface of the core zinc oxide particle, wherein the portion is less than the entirety of the surface of the core zinc oxide particle, wherein each of the multiple gold particles is a size of between five and ten nanometers, and wherein the core zinc oxide particle is 50-200 nanometers in size.
US Referenced Citations (60)
Number Name Date Kind
3761261 Ono et al. Sep 1973 A
3863007 Warner, Jr. Jan 1975 A
4549195 Bluzer Oct 1985 A
5011782 Lamb Apr 1991 A
5028417 Bhat et al. Jul 1991 A
5030699 Hendrickson Jul 1991 A
5147125 Austin Sep 1992 A
5223250 Mitchell Jun 1993 A
5441726 Mitchnick Aug 1995 A
5534056 Kuehnle Jul 1996 A
5553630 Dupuis Sep 1996 A
5902569 Oshima May 1999 A
5939054 Msika et al. Aug 1999 A
6419909 Lorant Jul 2002 B1
6534044 Wada Mar 2003 B1
6599355 Schmidt Jul 2003 B1
7143805 Weir Dec 2006 B1
7241399 Haubold Jul 2007 B2
7514863 Lee Apr 2009 B2
8647373 Shepherd Feb 2014 B1
9056063 Hanson Jun 2015 B2
9144535 Daly et al. Sep 2015 B1
9144536 Daly et al. Sep 2015 B1
9773931 Hossain Sep 2017 B2
20020122832 Hanke Sep 2002 A1
20030102099 Yadav Jun 2003 A1
20040209081 Hagihara Oct 2004 A1
20050008861 Yadav Jan 2005 A1
20050048010 Kliss Mar 2005 A1
20050208005 Giroud Sep 2005 A1
20050227063 Lawandy Oct 2005 A1
20050238600 Lien Oct 2005 A1
20050265935 Hollingsworth Dec 2005 A1
20060228310 Lyth Oct 2006 A1
20060241211 Coughlin Oct 2006 A1
20060270053 Tilak Nov 2006 A1
20070280895 Weimer Dec 2007 A1
20080107695 Fleissman May 2008 A1
20080149850 Tardif et al. Jun 2008 A1
20080181920 Buerger Jul 2008 A1
20080220026 Maltra Sep 2008 A1
20090022765 Chung Jan 2009 A1
20090061001 Hougaz Mar 2009 A1
20090104103 Bernstein Apr 2009 A1
20090258072 Schlossman Oct 2009 A1
20090258230 Schlossman Oct 2009 A1
20100008872 Katusic Jan 2010 A1
20100040567 Katusic Feb 2010 A1
20100055138 Margulies Mar 2010 A1
20100310871 McCormick Dec 2010 A1
20110268678 Armstrong Nov 2011 A1
20130006118 Pan Jan 2013 A1
20130039858 Brown Feb 2013 A1
20130216834 Hashimoto Aug 2013 A1
20140142213 Weiss May 2014 A1
20140242129 Gaurav Aug 2014 A1
20150283059 Nagare Oct 2015 A1
20160024688 Richardson et al. Jan 2016 A1
20160030304 Nagamatsu et al. Feb 2016 A1
20160082513 Niedermeyer Mar 2016 A1
Foreign Referenced Citations (20)
Number Date Country
103071535 May 2013 CN
104609459 May 2015 CN
1889810 Feb 2008 EP
09059591 Mar 1997 JP
2008024677 Feb 2008 JP
2011102291 May 2011 JP
2005023535 Mar 2005 WO
2008017176 Feb 2008 WO
2008079758 Jul 2008 WO
WO 2008079758 Jul 2008 WO
2011004133 Jan 2011 WO
2011089571 Jul 2011 WO
2012046204 Apr 2012 WO
2013040149 Mar 2013 WO
2013094639 Jun 2013 WO
2014040177 Mar 2014 WO
2014049139 Apr 2014 WO
2014077189 May 2014 WO
2016020168 Feb 2016 WO
WO 2016020168 Feb 2016 WO
Non-Patent Literature Citations (45)
Entry
U. Nobbmann, “FAQ: How important are refractive index & absorption for nanoparticles?” <http://www.materials-talks.com/blog/2014/08/05/faq-how-important-are-refractive-index-absorption-for-nanoparticles/> Materials Talks, Aug. 5, 2014, p. 1-2.
Family Health Team, “Best Ways to Protect Your Hair From Sun Damage,” Cleveland Clinic, health essentials, <https://health.clevelandclinic.org/2014/08/best-ways-to-protect-your-hair-from-sun-damage/>, published Aug. 22, 2014, p. 1-4.
List of IBM Patents or Applications Treated as Related.
Thokozane Moses Sithole, Synthesis and characterization of MBxOy:Eu (M=Ca, Sr, Ba) phosphors and TiO2 semiconductor for application in luminescence and energy materials, University of the Free State, Nov. 2014.
Sardar et al., Optical-absorption intensities and intermanifold emission cross sections of trivalent erbium ions in calcium fluorophosphate, Journal of Applied Physics, Sep. 2005.
Lu et al., 2008—White Up-Conversion Luminescence in Rare-Earth-Ion-Doped YAIO3 Nanocrystals, J. Phys. Chem. C 2008, 112, 15071-15074.
Refractive index of ZnO (Zinc oxide)—Bond-o, http://refractiveindex.info/?shelf=main&book=ZnO&page=Bond-o, Mar. 25, 2016.
Refractive index of SiO2 (Silicon dioxide, Silica, Quartz)—Malitson, http://refractiveindex.info/?shelf=main&book=SiO2&page=Malitson, Mar. 25, 2016.
Schubert et al., Design of multilayer antireflection coatings made from co-sputtered and low-refractive-index materials by genetic algorithm. Optics Express vol. 16, No. 8, 2008.
Law et al., ZnO—Al2O3 and ZnO—TiO2 Core-Shell Nanowire Dye-Sensitized Solar Cells. J. Phys. Chem. B 2006, 110, 22652-22663.
Pu et al., Core/shell structured ZnO/SiO2 nanoparticles: Preparation, characterization and photocatalytic property. Applied Surface Science 257 (2010) 393-397.
Mantz et al., Progress in Organic Coatings 47 (2003) 432-442, “A multiple-scattering model analysis of zinc oxide pigment for spacecraft thermal control coatings.”.
Song et al., Toxicology Letters 199 (2010) 389-397, “Role of the dissolved zinc io and reactive oxygen species in cytotoxicity of ZnO nanoparticles.”.
Bohren et al., “Absorption and Scattering of Light by Small Particles”, Wiley-VCH, © 2004, Weinheim.
Bae et al., J. Phys. Chem. B 2005, 109, 2526-2531, “Comparative Structure and Optical Properties of Ga-, In-, and Sn-Doped ZnO Nanowires Synthesized by thermal evaporation.”.
NanoComposix, Silver Nanoparticles: Optical Properties, http://nanocomposix.com/pages/silver-nanoparticles-optical-properties, Apr. 20, 2016.
Awazu et al., 2007—A Plasmonic Photocatalyst Consisting of Silver Nanoparticles Embedded in Titanium Dioxide, J. Am. Chem. Soc. 2008, 130, 1676-1680.
Sherry et al., Localized Surface Plasmon Resonance Spectroscopy of Single Silver Nanocubes, Nano Lett., vol. 5, No. 10, 2005.
Aguirre et al., Ag@ZnO Core_Shell Nanoparticles Formed by the Timely Reduction of Ag+ Ions and Zinc Acetate Hydrolysis in N,N-Dimethylformamide: Mechanism of Growth and Photocatalytic Properties, J. Phys. Chem. C 2011, 115, 24967-24974.
Haynes et al., Nanosphere Lithography: Tunable Localized Surface Plasmon Resonance Spectra of Silver Nanoparticles, J. Phys. Chem. B 2000, 104, 10549-10556.
U. Nobbmann, “FAQ: How important are refractive index & adsorption for nanoparticles?” http://www.materials-talks.com/blog/2014/08/05/faq-how-important-are-refractive-index-absorption-for-nanoparticles/ Materials Talks, Aug. 5, 2014, p. 1-2.
Tsuzuki et al., Nanoparticle Coatings for UV Protective Textiles, RJTA vol. 14 No. 2 2010.
Li et al., Transparent and Light-Emitting Epoxy Super-Nanocomposites Containing ZnO—QDs/SiO2 Nanocomposite Particles as Encapsulating Materials for Solid-State Lighting, J. Phys. Chem. C 2008, 112, 18616-18622.
Li et al., 2011—Sol-gel preparation and characterization of nanoporous ZnO_SiO2 coatings with broadband antireflection properties, Applied Surface Science 257 (2011) 9752-9756.
Messaoudi et al., “Synthesis and characterization of ZnO/Cu2O core-shell nanowires grown by two-step electrodeposition method.” Applied Surface Science 343 (2015) 148-152.
Luo et al., Facile synthesis of composition-tuned ZnO/ZnxCd1—xSe nanowires for photovoltaic applications, Nanoscale Research Letters (2015) 10:181.
Smijs et al. Titanium Dioxide and Zinc Oxide Nanoparticles in Sunscreens: Focus on Their Safety and Effectiveness, Nanotechnology, Science and Applications 4:95-112, Oct. 2011.
Wikipedia, List of Refractive Indices, last modified Feb. 15, 2017; https://en.wikipedia.org/wiki/List_of_refractive_indices.
Faure, B. et al. Dispersion and Surface Functionalization of Oxide Nanoparticles for Transparent Photocatalytic and UV-protecting Coatings and Sunscreens, Sci Technol. Adv. Mater. 14 2013, 023001.
Machine translation WO 2011/004133, printed 2017.
Wikipedia “Band Gap” last modified Jul. 18, 2017, https://en.wikipedia.org/wiki/Band_gap.
Machine translation WO 2012/046204, printed 2017.
Tariq Jan, et al. Sn Doping Induced Enhancement in the Activity of ZnO Nanostructures Against Antibiotic Resistant S. aureus Bacteria; Int J. Nanomedicine, vol. 8, pp. 3679-3687; Published online Sep. 30, 2013.
Bhatti et al. Optical Properties of Chromium & Cobalt Doped Zinc Oxide Powder Prepared by Sol-Gel Combustion Method, with the Assistance of Microwave Radiations; International Journal of Advanced Tech. in Engineering and Science; vol. 3, Issue 10; pp. 80-85; published Oct. 2015.
Cuprous Oxide, Chemical Book, pp. 1-4, Accessed Sep. 18, 2017, https://www.chemicalbook.com/ProductChemicalPropertiesCB9853041_EN.htm.
Simon Aldridge and Anthony Downs. The Group 13 Metals Aluminum, Gallium, Indium and Thallium Chemical Patterns and Peculiarities, 2011 John Wiley & Sons, Ltd., p. 623 (Year: 2011).
English language translation of WO 2013 094639 (A1) (Year: 2013).
Machine translation, JP 2008-024677, printer 2018.
Kelly et al. “The Optical Properties of Metal Nanoparticles: The Influence of Size, Shape and Dielectric Environment,” Journal of Physical Chemistry B 107:668-677, 2003.
Garcia, “Surface Plasmons in Metallic Nanoparticles: Fundamentals and Applications,” Journal of Physics D: Applied Physics 44(28), 283001, 2011.
Latha et al. “Sunscreening Agents: A Review,” Journal of Clinical and Aesthetic Dermatology 6(1):16-26, 2013.
Sreejith et al. “Squaraine Dyes: A Mine of Molecular Materials,” Journal of Materials Chemistry 18:264-274, 2008.
Merriam-Webster “Roughen.” Merriam-Webster.com, Merriam-Webster, n.d. Web. Aug. 22, 2018 (Year: 2018).
Naylor et al. “Sunscreens,” accessed 2017, http://telemedicine.org/sundam/sundam2.4.2.html.
Ultraviolet Radiation and the Intersun Programme [online]. WHO, Nov. 2003 [retrieved on Jun. 8, 2017]. Retrieved from the internet <http://www.who.int/uv/uv_and_health/en/>.
Related Publications (1)
Number Date Country
20170065507 A1 Mar 2017 US
Provisional Applications (1)
Number Date Country
62213686 Sep 2015 US