Electrical conducting polymer for Solar Cell and Hansen Solubility Parameters (HSP)

HSP Application note #66

2010.12.18

HSPiP Team Senior Developer, Dr. Hiroshi Yamamoto

Here is Electrical Conducting Polymer that contain Sulfur atom.

Polythiazyl

Polythiophene

Poly(3-alkyl thiophene)

Poly(2,5-thienylene vinylene)

Poly(isothianaphthene)

Poly(3,4-ethylenedioxythiophene)

Poly(1,4-bis(2-thienyl)-2,5-dialkoxyphenylene)

I got the solubility data for Poly(3-hexylthiophene) and Poly(3-docosylthiophene).

Hansen Solubility Parameters (HSP)

Hansen Solubility Parameters(HSP) were developed by Charles M. Hansen as a way of predicting if one material will dissolve in another and form a solution. They are based on the idea that "like dissolves like" where one molecule is defined as being 'like' another if it bonds to itself in a similar way.
Specifically, each molecule is given three Hansen parameters, each generally measured in MPa0.5:
dD:The energy from dispersion bonds between molecules
dP:The energy from dipolar intermolecular force between molecules
dH:The energy from hydrogen bonds between molecules.
These three parameters can be treated as Vector for a point in three dimensions also known as the Hansen space. The nearer two molecules HSP Vector are in this three dimensional space, the more likely they are to dissolve into each other.

What can perhaps be surprising is that one can assign HSP to so many different things. Gases like carbon dioxide, solids like carbon-60, sugar, and biological materials like human skin, depot fat, DNA, and even some proteins all have HSP. The list can be continued with drugs, polymers, plasticizers, and in fact any organic material and even many inorganic materials like salts. The only requirement for an experimental confirmation is that the material must behave differently in a sufficient number of test solvents upon contact.

Pirika JAVA Demo Applet calculate HSP. HSPLight is available here.
Please refer to e-Book of HSPiP if you want know more about HSP.
About the Power Tools that handle HSP more effectively.

Hcode	Solvent	Poly(3-hexylthiophene)	Score	Poly(3-docosylthiophene)	Score
48	anisole	◯△	1	X	0
92	1-butanol	X	0	X	0
122	carbontetrachloride	◯	1	◯	1
156	chloroform	◯	1	◯	1
219	di-n-butyl ether	△	0	X	0
306	1,4-dioxane	△	0	X	0
409	n-heptane	△	0	X	0
417	n-hexane	△	0	X	0
481	2-butanone	△	0	X	0
524	dichloromethane	◯△	1	X	0
619	tetrahydropyran	◯	1	◯△	1
637	toluene	◯△	1	◯△	1
649	trichloroethylene	◯	1	◯	1
697	p-xylene	◯△	1	◯	1
5336	N ,N'-dimethylaniline	◯	1	◯	1

With this solubility data, I can determine HSP of modified Poly-Thiophene with HSPiP.

HSPiP(Hansen Solubility Parameters in Practice)

The first edition of HSPiP that appeared in November, 2008, greatly enhanced the usefulness of the Hansen solubility parameters (HSP).

The HSP values of over 1200++ chemicals and 500 polymers are provided in convenient electronic format and have been revised and updated using the latest data sources in the second edition (March, 2009).

A third edition of the HSPiP appeared in March, 2010. There are now 10,000 compounds in the HSP file which also includes data on density, melting point, boiling point, critical parameters, Antoine constants and much more. The user is able to carry out many different sorts of optimisations of solubility, evaporation, diffusion, adhesion, create their own datasets (automatically if required) and explore the huge range of applications for HSP in coatings, paints, nanoparticles, cosmetics, pharma, organic photovoltaics and much more.

The 3rd Edition v3.1 was released on 12 December 2010. Current users can upgrade free (now v3.1.09) by downloading the latest .msi installer from http://hansen-solubility.com

The 4th Edition v4.0.x was released on 2 Jan. 2013. The Current users can upgrade with free charge.

2013.1.28 The Visual How to manual of HSPiP. You can understand what HSPiP can do.
Please check the Functional Group List whether your targets are available with HSPiP.
How to purchase HSPiP
2013..1.2 The HSPiP ver. 4 include Power Tools for HSPiP power user.

If I run the classic Sphere program, the HSP of Poly(3-HexylThiophene) become [19.1, 3.9, 6.4] Sphere radius 6.43.

Hansen Sphere

To determine if the parameters of two molecules (usually a solvent and a polymer) are within range a value called interaction radius (R0) is given to the substance being dissolved. This value determines the radius of the sphere in Hansen space and its center is the three Hansen parameters.

From version 3.1.X, Double Spheres function is available.

Pirika provide JAVA 3D Demo Applet to browse the Sphere(s).
The HTML5 Sphere Viewer examples are available here.
Now we have Power Tool "Sphere Viewer", GUI HTML5 software on HSPiP ver. 4.

For Poly(3-docosylThiophene), HSP become [17.9, 2.3, 3.4] and radius 3.39.
It is reasonable, as Alkyl chain become longer (6->22), dP and dH become smaller.
It is very important information if you want to design new solvents or mixture of solvents.
But we already have new technology!

Poly(3-HexylThiophene)

Poly(3-docosylThiophene)

Now we can use Double Spheres algorithm with HSPiP v. 3.1.x.

We can easily understand that modified poly-Thiophene have 2 regions.
One is Sphere A [17, 4.8, 6.1], the other is Sphere B [18.3, 1, 2].

Poly(3-HexylThiophene)
Sphere A: [17.8, 5.6, 6.2] Ra=3.27
Sphere B:[18.0, 0.2, 1.0] Ra=5.37

Poly(3-docosylThiophene)
Sphere A:[15.9, 4.2, 6.1] Ra=2.9
Sphere B:[18.5, 1.8, 3.4] Ra=4.05

let's browse Poly(3-HexylThiophene).

If you are using HTML5 enable browser such as Chrome, Safari or FireFox (IE9 is out of support), you will see the Canvas. If you pick solvent, solvent name will appear.

Please Use HTML5 Browser

Drag=Rotate, Drag+Shift=Larger/Smaller, Drag+Alt or Command(Window key)=Translate.

If search one sohere, [19.10, 4.61, 3.88] Ra=6.43

Please Use HTML5 Browser

Drag=Rotate, Drag+Shift=Larger/Smaller, Drag+Alt or Command(Window key)=Translate.

If search 2 spheres,
Sphere A: [17.8, 5.6, 6.2] Ra=3.27
Sphere B:[18.0, 0.2, 1.0] Ra=5.37

Poly(3-docosylThiophene) case,

Please Use HTML5 Browser

Drag=Rotate, Drag+Shift=Larger/Smaller, Drag+Alt or Command(Window key)=Translate.

one Sphere, [17.91, 2.3, 2.97] Ra=3.39

Please Use HTML5 Browser

Drag=Rotate, Drag+Shift=Larger/Smaller, Drag+Alt or Command(Window key)=Translate.

two spheres,
Sphere A:[15.9, 4.2, 6.1] Ra=2.9
Sphere B:[18.5, 1.8, 3.4] Ra=4.05

It is very strange to me, but Y-MB estimation result shows that Sphere B [18.3, 1, 2] is the main structure of polymer.
But Hexyl or Docosyl are very long alkyl chain. And those are very hydrophobic structure.
It is very difficult to understand where Sphere A [17, 4.8, 6.1] comes from.
If someone have plain solubility data of poly-Thiophene, please let me know.

In Classic Sphere, we explained that "if non solvent mixtures' HSP become polymer's HSP, it will dissolve". So both red an light blue mixture result in same.

If JAVA 3D is already installed in your machine, please try 3D view of this Sphere.

But now we can use double spheres, and I strongly recommend red solvents mixture for this polymer.

HSP of Solvents Mixture

[dDm, dPm, dHm]=[(a*dD1+b*dD2), (a*dP1+b*dP2),(a*dH1+b*dH2)]/(a+b)

Volume base ratio.

Pirika Java demo applet design solvents mixture. GSD is available here.

In this paper, they put C60 into polymer solution.
C60's HSP is [20, 3, 2] and very near to Main Structure of this polymer.
So this electric conducting polymer become very good binder of C60.

It is very good idea to use HSPiP for design of electric conducting polymer for Solar Cell binder.

Hansen Solubility Parameters(HSP) Application Notes

HSP Application note #66

Hansen Solubility Parameters (HSP)

HSPiP(Hansen Solubility Parameters in Practice)

Hansen Sphere

HSP of Solvents Mixture