Second-order Material Design - Revision history

Cmditradmin at 22:42, 3 November 2011

2011-11-03T22:42:17Z

Cmditradmin: /* Jen's Implementation of Diel-Alder Coupled Poling */

2010-07-19T22:39:49Z

Jen's Implementation of Diel-Alder Coupled Poling

← Older revision		Revision as of 15:39, 19 July 2010
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	[[Image:Alder_crosslinked.png\|thumb\|400px\|r33 stability of Dield-Alder Crosslinked Systems]]		[[Image:Alder_crosslinked.png\|thumb\|400px\|r33 stability of Dield-Alder Crosslinked Systems]]

	Dield-Alder Crosslinked Systems allows you to produce material that is a highly soluble polymer for purification and film casting (because of the protected maleimide, but then can be heated, deprotected, poled and locked into place with cross linking.		Dield-Alder Crosslinked Systems <ref>Zhengwei Shi, Steven Hau, Jingdong Luo, Tae-Dong Kim, Neil M. Tucker, Jae-Won Ka, Haishan Sun, Anna Pyajt, Larry Dalton, Antao Chen, and Alex K.-Y. Jen Advanced Functional Materials, Volume 17, Issue 14 (p 2557-2563)</ref> allows you to produce material that is a highly soluble polymer for purification and film casting (because of the protected maleimide, but then can be heated, deprotected, poled and locked into place with cross linking.

	These systems have a high r<sub>33</sub> are Thermally stable: ~80% of the original value can be retained at 70 °C for more than 250 hrs.		These systems have a high r<sub>33</sub> are Thermally stable: ~80% of the original value can be retained at 70 °C for more than 250 hrs.
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	== Lessons Learned ==		== Lessons Learned ==
	[[Image:hyperpol_year.JPG\|thumb\|400px\|Temporal Evolution of Poled Chromophores<ref>Larry Dalton, Philip Sullivan and Denise Bale, Electric Field Poled Organic Electro-optic Materials: State of the Art and Future Prospects Chem. Rev. 2010, 110, 25–55</ref>]]		[[Image:hyperpol_year.JPG\|thumb\|400px\|Temporal Evolution of Poled Chromophores<ref>Larry Dalton, Philip Sullivan and Denise Bale, Electric Field Poled Organic Electro-optic Materials: State of the Art and Future Prospects Chem. Rev. 2010, 110, 25–55</ref>]]

Cmditradmin: /* Lessons Learned */

2010-07-19T22:33:06Z

Lessons Learned

← Older revision		Revision as of 15:33, 19 July 2010
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	== Lessons Learned ==		== Lessons Learned ==
	[[Image:hyperpol_year.JPG\|thumb\|400px\|]]		[[Image:hyperpol_year.JPG\|thumb\|400px\|Temporal Evolution of Poled Chromophores<ref>Larry Dalton, Philip Sullivan and Denise Bale, Electric Field Poled Organic Electro-optic Materials: State of the Art and Future Prospects Chem. Rev. 2010, 110, 25–55</ref>]]
	These chromophores were not dramatically more non-linear than others, but they optimized the process for orienting them. The take home message is to not get hung up with just one property (eg r<sub>33</sub>) but to think about all the properties at once. If there is an existing establishing technology a small improvement will not lead people to abandon the old one. A factor of 10 improvement will stimulate change. The STC has lots of people over many institutions who calculate the theory, design the molecules, make the molecules, measure the properties of the molecules, process materials into materials, fabricate them into devices, and then integrate the devices into a system that actually does something. You can be part of a process that is bigger than the specific process you are working on. You will learn to appreciate the challenges that other specialists have and to be able to communicate and work together. This is the reward for working in an interdisciplinary group.		These chromophores were not dramatically more non-linear than others, but they optimized the process for orienting them. The take home message is to not get hung up with just one property (eg r<sub>33</sub>) but to think about all the properties at once. If there is an existing establishing technology a small improvement will not lead people to abandon the old one. A factor of 10 improvement will stimulate change. The STC has lots of people over many institutions who calculate the theory, design the molecules, make the molecules, measure the properties of the molecules, process materials into materials, fabricate them into devices, and then integrate the devices into a system that actually does something. You can be part of a process that is bigger than the specific process you are working on. You will learn to appreciate the challenges that other specialists have and to be able to communicate and work together. This is the reward for working in an interdisciplinary group.

Cmditradmin: /* Lessons Learned */

2010-07-19T21:55:48Z

Lessons Learned

← Older revision		Revision as of 14:55, 19 July 2010
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	[[Image:hyperpol_year.JPG\|thumb\|400px\|]]		[[Image:hyperpol_year.JPG\|thumb\|400px\|]]
	These chromophores were not dramatically more non-linear than others, but they optimized the process for orienting them. The take home message is to not get hung up with just one property (eg r<sub>33</sub>) but to think about all the properties at once. If there is an existing establishing technology a small improvement will not lead people to abandon the old one. A factor of 10 improvement will stimulate change. The STC has lots of people over many institutions who calculate the theory, design the molecules, make the molecules, measure the properties of the molecules, process materials into materials, fabricate them into devices, and then integrate the devices into a system that actually does something. You can be part of a process that is bigger than the specific process you are working on. You will learn to appreciate the challenges that other specialists have and to be able to communicate and work together. This is the reward for working in an interdisciplinary group.		These chromophores were not dramatically more non-linear than others, but they optimized the process for orienting them. The take home message is to not get hung up with just one property (eg r<sub>33</sub>) but to think about all the properties at once. If there is an existing establishing technology a small improvement will not lead people to abandon the old one. A factor of 10 improvement will stimulate change. The STC has lots of people over many institutions who calculate the theory, design the molecules, make the molecules, measure the properties of the molecules, process materials into materials, fabricate them into devices, and then integrate the devices into a system that actually does something. You can be part of a process that is bigger than the specific process you are working on. You will learn to appreciate the challenges that other specialists have and to be able to communicate and work together. This is the reward for working in an interdisciplinary group.

			see Dalton 2010 <ref>Larry Dalton, Philip Sullivan and Denise Bale, Electric Field Poled Organic Electro-optic Materials: State of the Art and Future Prospects Chem. Rev. 2010, 110, 25–55</ref>

	== References ==		== References ==

Cmditradmin at 20:20, 29 December 2009

2009-12-29T20:20:58Z

← Older revision		Revision as of 13:20, 29 December 2009
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	== References ==		== References ==
			[[category:second order NLO]]
	<references/>		<references/>
	<table id="toc" style="width: 100%">		<table id="toc" style="width: 100%">

Cmditradmin: /* Lessons Learned */

2009-11-30T17:42:29Z

Lessons Learned

← Older revision		Revision as of 10:42, 30 November 2009
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	== Lessons Learned ==		== Lessons Learned ==
	[[Image:hyperpol_year.JPG\|thumb\|~~300px~~\|]]		[[Image:hyperpol_year.JPG\|thumb\|400px\|]]
	These chromophores were not dramatically more non-linear than others, but they optimized the process for orienting them. The take home message is to not get hung up with just one property (eg r<sub>33</sub>) but to think about all the properties at once. If there is an existing establishing technology a small improvement will not lead people to abandon the old one. A factor of 10 improvement will stimulate change. The STC has lots of people over many institutions who calculate the theory, design the molecules, make the molecules, measure the properties of the molecules, process materials into materials, fabricate them into devices, and then integrate the devices into a system that actually does something. You can be part of a process that is bigger than the specific process you are working on. You will learn to appreciate the challenges that other specialists have and to be able to communicate and work together. This is the reward for working in an interdisciplinary group.		These chromophores were not dramatically more non-linear than others, but they optimized the process for orienting them. The take home message is to not get hung up with just one property (eg r<sub>33</sub>) but to think about all the properties at once. If there is an existing establishing technology a small improvement will not lead people to abandon the old one. A factor of 10 improvement will stimulate change. The STC has lots of people over many institutions who calculate the theory, design the molecules, make the molecules, measure the properties of the molecules, process materials into materials, fabricate them into devices, and then integrate the devices into a system that actually does something. You can be part of a process that is bigger than the specific process you are working on. You will learn to appreciate the challenges that other specialists have and to be able to communicate and work together. This is the reward for working in an interdisciplinary group.

Cmditradmin: /* Binary Chromophore Organic Glasses */

2009-11-30T17:41:49Z

Binary Chromophore Organic Glasses

← Older revision		Revision as of 10:41, 30 November 2009
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	BCOGs are formed by mixing two chromophore-containing materials (chromophores, dendrimers, or polymers) together.		BCOGs are formed by mixing two chromophore-containing materials (chromophores, dendrimers, or polymers) together.
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	[[Image:BCOG_r33.JPG\|thumb\|~~400px~~\|]]		[[Image:BCOG_r33.JPG\|thumb\|500px\|]]
	If you add two dendrimers the EO activity as a function of chromophore number density increases greatly. There are two possible reasons. There may be specifically spatially anisotropic interactions between the two components. The one chromophore is represented as a dipole with a three arm dendrimer. This a very energetically favorable interaction so it going to play a role. The electric field reacts with both components. It reduces the symmetry of organization of chromophores to 3dimensions to reduced dimensonality. The universal resolve is that order parameter as a function of poling energy is going to increase if you reduce the dimensionality of the latice that surrounds the chromophore.		If you add two dendrimers the EO activity as a function of chromophore number density increases greatly. There are two possible reasons. There may be specifically spatially anisotropic interactions between the two components. The one chromophore is represented as a dipole with a three arm dendrimer. This a very energetically favorable interaction so it going to play a role. The electric field reacts with both components. It reduces the symmetry of organization of chromophores to 3dimensions to reduced dimensonality. The universal resolve is that order parameter as a function of poling energy is going to increase if you reduce the dimensionality of the latice that surrounds the chromophore.

Cmditradmin: /* Dendrimer Approach */

2009-11-24T21:24:07Z

Dendrimer Approach

← Older revision		Revision as of 14:24, 24 November 2009
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	[[Image:Dendrimer.png\|thumb\|300px\|Schematic of generalized dendrimer arrangement]]		[[Image:Dendrimer.png\|thumb\|300px\|Schematic of generalized dendrimer arrangement]]
	A dendrimer is alike a tree with many branches. By attaching dendrimeric groups to the chromophore it is possible to have a high concentration without the loss associated with molecules being too close.		A dendrimer is alike a tree with many branches. By attaching dendrimeric groups to the chromophore it is possible to have a high concentration without the loss associated with molecules being too close.
			Through asymmetric shape modification and covalent chromophore attachment, high chromophore loading and r<sub>33</sub> can be achieved.
			[[Image:Dendrimer loading.png\|thumb\|300px\|Dendrimer loading vs order]]

			Even though steric and dielectric effects attenuate detrimental electrostatic effects, high density materials, such as dendrimers, theoretically and experimentally show poling-induced order, <cos<sup>3</sup>θ>, well below the theoretical limit.

	Possible variations:		Possible variations:
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	=== Dendrimer Encapsulated Chromophores ===		=== Dendrimer Encapsulated Chromophores ===
	[[Image:Dendrimer_encapsulated.png\|thumb\|300px\|Trifluorovinyl groups react at high temperature to form cross links]]		[[Image:Dendrimer_encapsulated.png\|thumb\|300px\|Trifluorovinyl groups react at high temperature to form cross links]]

Cmditradmin: /* Dendrimer Encapsulated Chromophores */

2009-11-24T21:16:10Z

Dendrimer Encapsulated Chromophores

← Older revision		Revision as of 14:16, 24 November 2009
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	=== Dendrimer Encapsulated Chromophores ===		=== Dendrimer Encapsulated Chromophores ===
	[[Image:Dendrimer_encapsulated.png\|thumb\|300px\|Trifluorovinyl groups react at high temperature to form cross links]]		[[Image:Dendrimer_encapsulated.png\|thumb\|300px\|Trifluorovinyl groups react at high temperature to form cross links]]
	Dendrimer encapsulated chromophores lead to large ~~rlectro~~-optic voefficient and high thermal stability		Dendrimer encapsulated chromophores lead to large electro-optic voefficient and high thermal stability

	Jen and Dalton have created dendrimeric systems with trifluorovinyl groups (shown in red). These can react with each other at high temperature (170 deg) to form cyclobutanes. When the molecules are heated and poled the groups cross link and lock the chromophore into orientation.		Jen and Dalton have created dendrimeric systems with trifluorovinyl groups (shown in red). These can react with each other at high temperature (170 deg) to form cyclobutanes. When the molecules are heated and poled the groups cross link and lock the chromophore into orientation.
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	See Jen 2001 <ref>Jen & Dalton et al., J. Am. Chem Soc. 123, 986 (2001)</ref>		See Jen 2001 <ref>Jen & Dalton et al., J. Am. Chem Soc. 123, 986 (2001)</ref>

	=== Binary Chromophore Organic Glasses ===		=== Binary Chromophore Organic Glasses ===

Cmditradmin: /* Generalized Chromophore */

2009-11-24T18:10:11Z

Generalized Chromophore

← Older revision		Revision as of 11:10, 24 November 2009
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	In terms of complexity these chemicals are beginning to look less like dyes and more like pharmaceuticals.		In terms of complexity these chemicals are beginning to look less like dyes and more like pharmaceuticals.
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			Density function theory can be used to visualize this change in electron density in the presence of an electric field. It will be somewhere between the HOMO and the LUMO state seen here.
			[[Image:Dft chromophore homolumo.png\|thumb\|300px\|DFT model of LUMO and HOMO states]]

	=== Enhanced Stability with Diarylamino Donor ===		=== Enhanced Stability with Diarylamino Donor ===
	[[Image:Diarylamino_donor.png\|thumb\|300px\|Diarylamino Donor]]		[[Image:Diarylamino_donor.png\|thumb\|300px\|Diarylamino Donor]]

← Older revision		Revision as of 15:42, 3 November 2011
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	=== Polar chromophore in polar host ===		=== Polar chromophore in polar host ===

	If you put a chromophore in an off-the-shelf polymer like polycarbonates or polyacrilinides, and you increase the concentration it will phase-separate, and the optical loss scattering will go up. The EO will disappear because of symmetry aggregation. It will also line-broaden and red shift because the dielectric environment around the chromophore is changing. When you put a polar object in a non-polar medium you have a lousy enthalpy of mixing, while your entropy of mixing is improved because you are mixing two disparate objects. But if you put a polar object in a polar host you have great enthalpy and good entropy of mixing, you get no spectral line broadening as a function of concentration, and you get no solvatochromic shifts. So not only is your EO activity improved but the optical loss is optimim because you aren’t getting any optical absorption at the telecommunication wavelengths, ~~your~~ not getting phase separation so there is no scattering and your optical transparency is excellent.		If you put a chromophore in an off-the-shelf polymer like polycarbonates or polyacrilinides, and you increase the concentration it will phase-separate, and the optical loss scattering will go up. The EO will disappear because of symmetry aggregation. It will also line-broaden and red shift because the dielectric environment around the chromophore is changing. When you put a polar object in a non-polar medium you have a lousy enthalpy of mixing, while your entropy of mixing is improved because you are mixing two disparate objects. But if you put a polar object in a polar host you have great enthalpy and good entropy of mixing, you get no spectral line broadening as a function of concentration, and you get no solvatochromic shifts. So not only is your EO activity improved but the optical loss is optimim because you aren’t getting any optical absorption at the telecommunication wavelengths, you're not getting phase separation so there is no scattering and your optical transparency is excellent.

	=== Comparison of Thermal Stabilities ===		=== Comparison of Thermal Stabilities ===
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	=== Post Functionalization Approach ===		=== Post Functionalization Approach ===
	[[Image:Postfunctionalization.png\|thumb\|300px\|Dyes can be attached after the polyimid polymer is formed]]		[[Image:Postfunctionalization.png\|thumb\|300px\|Dyes can be attached after the polyimid polymer is formed]]
	Another way to improve the stability of the system is by attaching the material to the host. Polyimid is a high temperature polymer. Alex Jen incorporated functional groups and then added a dye with a hydroxyl group. He attached the dye after the material was polymerized because the conditions for forming the polymer are quite harsh.		Another way to improve the stability of the system is by attaching the material to the host. Polyimid is a high temperature polymer. Alex Jen incorporated functional groups and then added a dye with a hydroxyl group. He attached the dye after the material was polymerized because the conditions for forming the polymer are quite harsh.

	=== High Glass Transition Polymer Approach ===		=== High Glass Transition Polymer Approach ===
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	[[Image:Dendrimer loading.png\|thumb\|300px\|Dendrimer loading vs order]]		[[Image:Dendrimer loading.png\|thumb\|300px\|Dendrimer loading vs order]]

	Even though steric and dielectric effects attenuate detrimental electrostatic effects, high density materials, such as dendrimers, theoretically and experimentally show poling-induced order, <cos<sup>3</sup>θ>, well below the theoretical limit.		Even though steric and dielectric effects attenuate detrimental electrostatic effects, high density materials, such as dendrimers, theoretically and experimentally show poling-induced order, <cos<sup>3</sup>θ>, well below the theoretical limit.

	Possible variations:		Possible variations:
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	[[Image:BCOG_r33.JPG\|thumb\|500px\|]]		[[Image:BCOG_r33.JPG\|thumb\|500px\|]]
	If you add two dendrimers the EO activity as a function of chromophore number density increases greatly. There are two possible reasons. There may be specifically spatially anisotropic interactions between the two components. The one chromophore is represented as a dipole with a three arm dendrimer. This a very energetically favorable interaction so it going to play a role. The electric field reacts with both components. It reduces the symmetry of organization of chromophores to 3dimensions to reduced ~~dimensonality~~. The universal resolve is that order parameter as a function of poling energy is going to increase if you reduce the dimensionality of the ~~latice~~ that surrounds the chromophore.		If you add two dendrimers the EO activity as a function of chromophore number density increases greatly. There are two possible reasons. There may be specifically spatially anisotropic interactions between the two components. The one chromophore is represented as a dipole with a three arm dendrimer. This a very energetically favorable interaction so it going to play a role. The electric field reacts with both components. It reduces the symmetry of organization of chromophores to 3dimensions to reduced dimensionality. The universal resolve is that order parameter as a function of poling energy is going to increase if you reduce the dimensionality of the lattice that surrounds the chromophore.

	To test this idea we conducted laser assisted poling. We use a polarized laser light to selectively change the orientation of one our two components in the mixture and look at the change on the other component. We are able to see a factor of 2.5 change of the order of this chromophore as function of changing the other. This proves that there must be an electrostatic interaction between the components. This is exciting for several reasons. It allows you to achieve a dramatic increase in EO activity by exploiting the interaction between the components. For the first time you are able to directly measure the electrostatic interaction between components in a multicomponent mixture.		To test this idea we conducted laser assisted poling. We use a polarized laser light to selectively change the orientation of one our two components in the mixture and look at the change on the other component. We are able to see a factor of 2.5 change of the order of this chromophore as function of changing the other. This proves that there must be an electrostatic interaction between the components. This is exciting for several reasons. It allows you to achieve a dramatic increase in EO activity by exploiting the interaction between the components. For the first time you are able to directly measure the electrostatic interaction between components in a multicomponent mixture.

	By using variable angle polarized absorption spectrometry you can see that the bands of different components do not overlap. You can measure the order parameter for each, change the order parameter on one and then see change on the other. From this you can back out the electrostatic potential.		By using variable angle polarized absorption spectrometry you can see that the bands of different components do not overlap. You can measure the order parameter for each, change the order parameter on one and then see change on the other. From this you can back out the electrostatic potential.

	=== Performance Comparison of Various NLO Materials ===		=== Performance Comparison of Various NLO Materials ===