The present disclosure relates to active matrix arrays and elements thereof.
In a particular aspect, the present disclosure relates to digital microfluidics, and more specifically to Electrowetting on Dielectric (EWOD) devices such as Active Matrix Electrowetting on Dielectric (AM-EWOD) devices. The disclosure further relates to fluids that enable low-voltage operation of such devices.
Electrowetting on Dielectric (EWOD) is a technique for manipulating droplets of fluid by application of an electric field. It is thus a candidate technology for digital microfluidics for lab-on-a-chip technology. An introduction to the basic principles of this technology can be found in “Digital microfluidics: is a true lab-on-a-chip possible?” R. B. Fair, Microfluid Nanofluid (2007) 3:245-281.
The filler fluid 8 is typically non-polar and immiscible, or substantially immiscible with the liquid droplet 1 being manipulated. An insulator layer 5 disposed upon the lower substrate 12 separates the conductive element electrodes 10A and 10B from a first hydrophobic coating 3 upon which the liquid droplet 1 sits with a contact angle 2 represented by θ. The first hydrophobic coating 3 is formed from a hydrophobic material (commonly, but not necessarily, a fluoropolymer).
On the top substrate 9 is a second hydrophobic coating 4 with which the liquid droplet 1 may come into contact. The second hydrophobic coating 4 is formed from a hydrophobic material (commonly, but not necessarily, a fluoropolymer). Interposed between the top substrate 9 and the second hydrophobic coating 4 is a reference electrode 6.
The contact angle θ2 of the liquid droplet 1 and the first hydrophobic coating 3 is defined as shown in
In operation, voltages termed the EW drive voltages (e.g. VT, V0 and V00 in
The Lippmann-Young equation, shown below in equation 2, describes how the electrowetting voltage (V) affects the contact angle. In equation 2, C is the capacitance of the insulator layer 5 and hydrophobic coating 3 which forms the interface between the droplet 1 and the hydrophobic surface, 80 is the contact angle when no voltage is applied, and γLG is the surface tension component of the non-ionic fluid/droplet.
Active Matrix EWOD (AM-EWOD) refers to implementation of EWOD in an active matrix array incorporating transistors, for example by using thin film transistors (TFTs).
U.S. Pat. No. 6,565,727 (Shenderov, issued May 20, 2003) discloses a passive matrix EWOD device for moving droplets through an array. U.S. Pat. No. 6,565,727 further discloses methods for other droplet operations including the splitting and merging of droplets, and the mixing together of droplets of different materials.
U.S. Pat. No. 6,911,132 (Pamula et al., issued Jun. 28, 2005) discloses a two dimensional EWOD array to control the position and movement of droplets in two dimensions.
U.S. Pat. No. 7,163,612 (Sterling et al., issued Jan. 16, 2007) describes how TFT based thin film electronics may be used to control the addressing of voltage pulses to an EWOD array by using circuit arrangements very similar to those employed in AM display technologies. The approach of U.S. Pat. No. 7,163,612 may be termed “Active Matrix Electrowetting on Dielectric” (AM-EWOD).
European Patent Application No. EP2404675 (Hadwen et al., published Jan. 11, 2012) describes array element circuits for an AM-EWOD device.
The addition of a surfactant is known to greatly enhance the electrowetting effect as described by O. Raccurt et. al. (J. Micromech. Microeng. 17 (2007) 2217-2223).
U.S. Pat. No. 8,481,125 (Yi et al., issued Jul. 9, 2013) describes how certain lipophilic polymers can be used to reduce biofouling in electrowetting devices. Biofouling is a process where chemicals or bio molecules adhere undesirably to a surface.
The use of surfactants which are soluble in the filler fluid of an electrowetting system is described by L. S. Roach et al. (Analytical Chemistry, 2005, 77(3), 785-796).
U.S. Pat. No. 8,980,198 (Srinivasan et al., issued Mar. 17, 2015) lists some possible surfactants that are soluble in the filler fluid and may be used in electrowetting devices.
In accordance with one aspect of the present disclosure, an electrowetting on dielectric device, includes: (a) a first substrate including electrodes at a surface of the first substrate configured to effect electrowetting mediated droplet operations; (b) a second substrate spaced from the surface of the first substrate to define an interior volume between the first substrate and the second substrate; (c) a liquid droplet disposed in the interior volume; and (d) a filler fluid disposed in the interior volume and surrounding the liquid droplet, wherein one or both of the liquid droplet and filler fluid contains a surfactant, the surfactant including a siloxane group represented by the structural formula:
where n≧1.
In some embodiments, the surfactant is provided at a concentration ranging from about 0.001 to about 10% w/w in the liquid droplet or the filler fluid.
In some embodiments, the filler fluid includes a silicone oil.
In some embodiments, the filler fluid includes:
where 7>n>1.
In some embodiments, the filler fluid includes a hydrocarbon oil.
In some embodiments, the surfactant has no overall charge.
In some embodiments, the surfactant is anionic or cationic.
In some embodiments, the surfactant further includes a polyol.
In some embodiments, the surfactant further includes polyethylene glycol.
In some embodiments, the surfactant further includes polyoxyethylene glycol (—(CH2CH2—O—)n) where n≧1.
In some embodiments, the surfactant further includes polyoxypropylene glycol (—(CH2CHCH3—O—)n) where n≧1.
In some embodiments, the surfactant further includes a hydrocarbon chain (CH2)n where n≧1.
In some embodiments, the surfactant is represented by the structural formula:
wherein a≧1, b≧1, c≧1, and d≧1; and R═—H or —CH3.
In some embodiments, the surfactant is represented by the structural formula:
wherein a≧1, b≧1, c≧1, d≧1, and e≧1; and R═—H or —CH3.
In some embodiments, the surfactant is represented by the structural formula:
wherein a≧1 and b≧1; and R═—H or —CH3.
In some embodiments, the surfactant is represented by the structural formula:
wherein a≧1, b≧1, and c≧1; and R═—H or —CH3.
In some embodiments, the surfactant is represented by the structural formula:
wherein a≧1, b≧1, c≧1, d≧1, e≧1 and f≧1; and R═—H or —CH3.
In some embodiments, the filler fluid contains the surfactant, the surfactant soluble in the filler fluid. In some embodiments, the liquid droplet contains an additional surfactant.
In some embodiments, the liquid droplet contains the surfactant and the surfactant is soluble in the liquid droplet.
To the accomplishment of the foregoing and related ends, the invention, then, comprises the features hereinafter fully described and particularly pointed out in the claims. The following description and the annexed drawings set forth in detail certain illustrative embodiments of the invention. These embodiments are indicative, however, of but a few of the various ways in which the principles of the invention may be employed. Other objects, advantages and novel features of the invention will become apparent from the following detailed description of the invention when considered in conjunction with the drawings.
In the annexed drawings, like references indicate like parts or features:
1 liquid droplet
2 contact angle θ
3 First hydrophobic coating
4 Second hydrophobic coating
5 Insulator layer
6 Reference electrode
7 Spacer
8 Filler fluid
9 Top substrate
10, 10A, 10B Array Element Electrodes
11 Electrode array
12 Lower substrate
13 Thin film electronics
The AM-EWOD device shown in
In some embodiments, the surfactant (e.g., contained within the filler fluid 8) may contain a siloxane functional group represented by the following structural formula A.
The surfactant may contain one or more siloxane units. Hence, the surfactant may be regarded as containing one or more siloxane groups which may be represented by the following structural formula B:
where n≧1.
Surfactants containing structural formulas A or B may provide one or more advantages in electrowetting devices, including:
These advantages may enable AM-EWOD devices to perform a wide range of commercially relevant (bio)chemical transformations which would have otherwise been elusive.
Generally, an exemplary AM-EWOD device that includes thin film electronics 13 is configured as follows. The AM-EWOD device includes a reference electrode 6 (e.g., an in-plane reference electrode 6) and a plurality of array elements, each array element including an array element electrode (e.g., array element electrodes 10).
Relatedly, the AM-EWOD device may be configured to perform a method of controlling an electrowetting voltage to be applied to a plurality of array 11 elements. The AM-EWOD may include reference electrode 6 and a plurality of array elements, each array element including an array element electrode 10. The electrowetting voltage at each array element may be defined by a potential difference between the array element electrode 10 and the reference electrode 6. The method of controlling the electrowetting voltage includes the steps of writing a voltage to at least a portion of the array element electrodes 10, and supplying a voltage signal to the reference electrode 6.
In operation the AM-EWOD device may be configured to perform droplet operation in accordance with the sequence by which the element electrodes are activated. Exemplary droplet operations include:
In order for the AM-EWOD device to carry out this range of operations, a large change in contact angle should be able to result from a small electrowetting voltage. For this reason, it may be preferable and advantageous to use a surfactant within the system to lower the surface tension and reduce the electrowetting voltage.
In AM-EWOD devices it may be particularly desirable and advantageous to reduce the electrowetting voltage in order to facilitate droplet manipulation at electrowetting voltages that are compatible with the maximum ratings of standard TFT devices (e.g., fabricated by standard Liquid Crystal Display manufacturing process). Possible technologies for fabricating the TFT backplane may include polysilicon TFT, oxide TFT (e.g. Indium Gallium Zinc Oxide TFT), amorphous silicon TFTs or organic TFTs.
It may also be advantageous to minimize the electrowetting voltage in order to reduce the power consumed by the TFT circuitry. Furthermore, it may be advantageous to minimize the electrowetting voltage to reduce the electric field through the insulator and hydrophobic coating layers included as part of the AM-EWOD device. This may improve device reliability and manufacturing.
In some embodiments, the AM-EWOD device may be operated with oil as the filler fluid. The advantages of using an oil (rather than air) are:
Whilst in principle EWOD devices can use a number of different of oils for the filler fluid, there are practical considerations that may make certain materials preferable. These include:
The inventors have found that silicone oils in general may fulfill one or more of the above-described criteria. Silicone oils include a group represented by the following structural formula C:
wherein n≧1 and R is H—, CH3—, CH3CH2—, Phenyl- (H5C6—), Benzyl- (H5C6CH2—), Tolyl- (CH3H5C6—), a partially or fully fluorinated alkyl or another suitable functional group.
The silicone oil may also have a cyclic structure as in for example decamethylcyclopentasiloxane.
Silicone oils may be used as lubricants and hydraulic fluids due to being non-flammable unlike their carbon analogues. In addition, silicone oils are excellent electrical insulators, have good temperature stability and have good heat-transfer characteristics.
More specifically, the inventors have found that silicone oils represented by the following structural formula D may be suited to AM-EWOD application, as such silicone oils may further fulfill the above described criteria for volatility and/or viscosity:
where 7>n>1.
The AM-EWOD devices in accordance with the present disclosure may be operated with a surfactant included in either the oil or the liquid droplet. The use of a surfactant may lower the surface tension and may facilitate droplet operations at low voltage.
There may be several advantages of using surfactants which are soluble in the filler fluid. These include:
One issue with the use of silicone oil is that many conventional surfactants are insoluble in silicone oils even at low concentration. But in accordance with the present disclosure, the inventors have found that surfactants containing siloxane units as described above in connection with structural formulas A and B may be soluble in silicone oils and utilized as the surfactant in connection with the EWOD device. The present disclosure thus realizes a filler fluid including a combination of an oil material and a surfactant that may have several advantageous properties. These properties may be particularly advantageous for AM-EWOD systems where achieving a low electrowetting voltage is desirable.
In some embodiments, the filler fluid may contain the surfactant at a concentration ranging from about 0.001 to about 15% w/w. In other embodiments, the filler fluid may contain the surfactant at a concentration ranging from about 0.001 to about 10% w/w. In other embodiments, the filler fluid may contain the surfactant at a concentration ranging from about 0.001 to about 5% w/w.
There are a large number of possible surfactant chemical structures that may include the siloxane unit as described above in connection with structural formulas A and B. Surfactant structures include a hydrophobe (hydrophobic group) coupled to a polar (hydrophilic) functional group. It is the coupling of the hydrophobic and hydrophilic groups that give the surfactant structure its distinctive properties, for example lowering surface tension. In accordance with the present disclosure, the siloxane unit is used to form the hydrophobe of the surfactant structure. There are many possible polar (hydrophilic) groups which may be coupled to the siloxane unit to create a surfactant. In some embodiments, the hydrophilic group may be a polyol. One example of a hydrophilic group is a polyethylene glycol. In other embodiments, the hydrophilic group may be a polyoxyethylene glycol (—(CH2CH2—O—)n) where n≧1, a polyoxypropylene glycol (—(CH2CHCH3—O—)n) where n≧1, or may contain sugars or their derivatives.
In some embodiments, one or more hydrocarbon chains (CH2)n (where) n≧1) may be incorporated with the hydrophobe to further increase the hydrophobicity of the hydrophobe. The hydrocarbon chain may be a straight chain, branched or contain cyclic units, and may contain aromatic and other unsaturated sub units. The hydrophobic group may contain some polar groups such as (—OH, ═NH, ═C═O, —CO2H, —CN, —C—O—C—, —C—NH—C) while still being hydrophobic overall. The hydrocarbon chain may, in some embodiments, connect the hydrophobe with the hydrophilic group.
In some embodiments, the surfactant may include one or more functional groups with a positive charge such as quaternary amines (—N+R3), phosphonium salts (—PR3+) and sulfonium salts (—SR2+); R is H—, CH3—, CH3CH2—, Phenyl- (H5C6—), Benzyl- (H5C6CH2—), Tolyl- (CH3H5C6—), a partially or fully fluorinated alkyl or other suitable group. In some embodiments, the surfactant may include one or more functional groups with a negative charge such as sulfates (—OSO3−), sulfonates (—SO3−), phosphates (—OPO32−) and carboxylates (—CO2−). Such surfactants may have no overall charge, and in such instances may be referred to as zwitterionic surfactants. These charged groups can be incorporated into the surfactant via direct connection to the siloxane backbone or via a connecting chain such as an alkyl chain or glycol chain.
In some embodiments, the surfactant has no overall charge. In other embodiments, the surfactant is anionic. In other embodiments, the surfactant is cationic.
The following description sets forth several exemplary surfactants containing siloxane unit(s) in accordance with the present disclosure. The structures of the surfactants containing siloxane unit(s) described below are exemplary and should not be understood to be limiting the scope of the present disclosure.
One exemplary class of surfactants containing siloxane unit(s) combines the siloxane group (e.g., dimethylsiloxane) with a polyol, an example of which is represented by the following structural formula (E).
where a≧1, b≧1, c≧1 and d≧1; and R is H—, CH3—, CH3CH2—, Phenyl- (H5C6—), Benzyl- (H5C6CH2—), Tolyl- (CH3H5C6—), a partially or fully fluorinated alkyl or other suitable group.
The values of a, b, c and d can be varied to change the total hydrophobicity of the surfactant. For example, increasing a and c may increase the hydrophobicity of the surfactant containing the siloxane unit(s) shown in structural formula (E).
Increasing b and d may reduce the hydrophobicity of the surfactant containing the siloxane unit(s) shown in structural formula (E).
Another exemplary class of surfactants containing siloxane unit(s) incorporate a polyoxypropylene glycol (—(CH2CHCH3—O—)n) chain, examples of which are represented by the following structural formulas (F) and (G), respectively:
where a≧1, b≧1, c≧1, and d≧1; and R is H—, CH3—, CH3CH2—, Phenyl- (H5C6—), Benzyl- (H5C6CH2—), Tolyl- (CH3H5C6—), a partially or fully fluorinated alkyl or other suitable group.
In structural formula (F), the values of a, b, c, and d can be varied to change the total hydrophobicity of the surfactant. For example, increasing a and c may increase the hydrophobicity of the surfactant containing the siloxane unit(s) shown in structural formula (F). Increasing b, and d may reduce the hydrophobicity of the surfactant containing the siloxane unit(s) shown in structural formula (F).
where a≧1, b≧1, c≧1 d≧1 and e≧1; and R is H—, CH3—, CH3CH2—, Phenyl- (H5C6—), Benzyl- (H5C6CH2—), Tolyl- (CH3H5C6—), a partially or fully fluorinated alkyl or other suitable group.
In structural formula (G), the values of a, b, c, d and e can be varied to change the total hydrophobicity of the surfactant. For example, increasing a and c may increase the hydrophobicity of the surfactant containing the siloxane unit(s) shown in structural formula (G). Increasing b, d and e may reduce the hydrophobicity of the surfactant containing the siloxane unit(s) shown in structural formula (G).
Another exemplary class of surfactants containing siloxane unit(s) may be implemented as a triblock polymer, an example of which is represented by the following structural formulae (H) and (I):
where a≧1, b≧1 and c≧1; R is H—, CH3—, CH3CH2—, Phenyl- (H5C6—), Benzyl- (H5C6CH2—), Tolyl- (CH3H5C6—), a partially or fully fluorinated alkyl or other suitable group.
where a≧1, b≧1 and c≧1; and R is H—, CH3—, CH3CH2—, Phenyl- (H5C6—), Benzyl- (H5C6CH2—), Tolyl- (CH3H5C6—), a partially or fully fluorinated alkyl or other suitable group.
The values of a, b and c can be varied to change the total hydrophobicity of the surfactant. For example, increasing a and b may increase the hydrophobicity of the surfactant containing the siloxane unit(s) shown in structural formula (H). Increasing c may reduce the hydrophobicity of the surfactant containing the siloxane unit(s) shown in structural formula (H). In structural formula (I) the values of a, b and c can be varied to change the total hydrophobicity of the surfactant. For example, increasing a and b may increase the hydrophobicity of the surfactant containing the siloxane unit(s) shown in structural formula (I). Increasing c may reduce the hydrophobicity of the surfactant containing the siloxane unit(s) shown in structural formula (I).
Another exemplary class of surfactants containing siloxane unit(s) may include a hydrocarbon chain (e.g., a lipophilic chain) to increase its solubility in the filler fluid, examples of which is represented by the following structural formulae (J and K). The structural formulae (J and K) combine the siloxane group with a polyol, wherein a hydroxyl terminated group is included on the hydrophilic tale.
where a≧1, b≧1, c≧1, d≧1, e≧, and f≧1; and R is H—, CH3—, CH3CH2—, Phenyl- (H5C6—), Benzyl- (H5C6CH2—), Tolyl- (CH3H5C6—), a partially or fully fluorinated alkyl or other suitable group.
where a≧1, b≧1, c≧1, d≧1, e≧, f≧1 and g≧1; and R is H—, CH3—, CH3CH2—, Phenyl- (H5C6—), Benzyl- (H5C6CH2—), Tolyl- (CH3H5C6—), a partially or fully fluorinated alkyl or other suitable group.
The values of a, b, c, d, e, f and g can be varied to change the total hydrophobicity of the surfactant. For example, increasing a, b, d and e may increase the hydrophobicity of the surfactant containing the siloxane unit(s) shown in structural formula (J). Increasing c and f may reduce the hydrophobicity of the surfactant containing the siloxane unit(s) shown in structural formula (J).
Increasing a, b, d and e may increase the hydrophobicity of the surfactant containing the siloxane unit(s) shown in structural formula (K). Increasing c, f and g may reduce the hydrophobicity of the surfactant containing the siloxane unit(s) shown in structural formula (K).
Other examples of surfactants containing siloxane unit(s) are set forth below in structural formulas (L)-(Q):
where a≧1 and b≧1.
where a≧1 and b≧1.
where a≧1, b≧1, c≧ and d≧1.
where a≧1, b≧1, c≧1, d≧1, e≧1 and f≧1.
where a≧1, and b≧1; and R is H—, CH3—, CH3CH2—, Phenyl- (H5C6—), Benzyl- (H5C6CH2—), Tolyl- (CH3H5C6—), a partially or fully fluorinated alkyl or other suitable group.
where a≧1, and b≧1; and R is H—, CH3—, CH3CH2—, Phenyl- (H5C6—), Benzyl- (H5C6CH2—), Tolyl- (CH3H5C6—), a partially or fully fluorinated alkyl or other suitable group.
In structural formula (L) the values of a and b can be varied to change the total hydrophobicity of the surfactant. For example, increasing a may increase the hydrophobicity of the surfactant containing the siloxane unit(s) shown in structural formula (L). Increasing b may reduce the hydrophobicity of the surfactant containing the siloxane unit(s) shown in structural formula (L).
In structural formula (M) the values of a and b can be varied to change the total hydrophobicity of the surfactant. For example, increasing a may increase the hydrophobicity of the surfactant containing the siloxane unit(s) shown in structural formula (M). Increasing b may reduce the hydrophobicity of the surfactant containing the siloxane unit(s) shown in structural formula (M).
In structural formula (N) the values of a, b, c and d can be varied to change the total hydrophobicity of the surfactant. For example, increasing a, b and d may increase the hydrophobicity of the surfactant containing the siloxane unit(s) shown in structural formula (N). Increasing c may reduce the hydrophobicity of the surfactant containing the siloxane unit(s) shown in structural formula (N).
In structural formula (O) the values of a, b, c, d e and f can be varied to change the total hydrophobicity of the surfactant. For example, increasing a, b and d may increase the hydrophobicity of the surfactant containing the siloxane unit(s) shown in structural formula (O). Increasing c, e and f may reduce the hydrophobicity of the surfactant containing the siloxane unit(s) shown in structural formula (O).
In structural formula (P) the values of a and b can be varied to change the total hydrophobicity of the surfactant. For example, increasing a may increase the hydrophobicity of the surfactant containing the siloxane unit(s) shown in structural formula (P). Increasing b may reduce the hydrophobicity of the surfactant containing the siloxane unit(s) shown in structural formula (P).
In structural formula (Q) the values of a and b can be varied to change the total hydrophobicity of the surfactant. For example, increasing a may increase the hydrophobicity of the surfactant containing the siloxane unit(s) shown in structural formula (Q). Increasing b may reduce the hydrophobicity of the surfactant containing the siloxane unit(s) shown in structural formula (Q).
As described above, the siloxane containing surfactants may provide advantageous properties over conventional surfactants, particularly in AM-EWOD systems where achieving a low electrowetting voltage is desirable.
In embodiments described above, the siloxane surfactant may be soluble in the silicone oil. In some embodiments, the siloxane surfactant is water soluble; this may be achieved by increasing the wt. % of the hydrophilic portion of the surfactant. Such embodiments may still provide a low surface tension siloxane surfactant. In such embodiments, the surfactant may be incorporated into the aqueous droplet. This may make it possible to increase the speed at which the droplets can be moved.
In some embodiments, the liquid droplet may contain the surfactant at a concentration ranging from about 0.001 to about 15% w/w. In other embodiments, the liquid droplet may contain the surfactant at a concentration ranging from about 0.001 to about 10% w/w. In other embodiments, the liquid droplet may contain the surfactant at a concentration ranging from about 0.001 to about 5% w/w.
In embodiments described above, the oil utilized is a silicone oil. In some embodiments, the oil may be a hydrocarbon oil material with the siloxane surfactant dissolved in it. Such embodiments may retain the advantages of the above-described embodiments while also enabling a wider range of oils to be used, thereby increasing the flexibility of the device to perform a range of chemistries. Some examples of hydrocarbon oils that may be utilized as the oil material in which the siloxane surfactant is dissolved include octane, decane, dodecane, tetradecane, hexadecane, and xylene.
In embodiments described above, the siloxane surfactant may be the only surfactant provided in the oil or liquid droplet. In some embodiments, one or more surfactants additional to the siloxane may be included in the oil and/or liquid droplet. The additional surfactants may be soluble in either the oil or the liquid droplet. In some embodiments where the siloxane surfactant is provided in the oil, the additional surfactant(s) may be provided in the liquid droplet. In embodiments where the siloxane surfactant is provided in the liquid droplet, the additional surfactant(s) may be provided in the oil. Exemplary additional surfactants may be block copolymers based on ethylene oxide and propylene oxide (Pluoronic®), polyethoxylated sorbitan esters (Tween®), Sorbitan esters (Span®), polyoxyethylene glycol alkyl ethers (Brij®) and such like. One example of an additional surfactant is a poly(ethylene glycol)-poly(propylene glycol)-poly(ethylene glycol) triblock polymer.
The described embodiments may be used to provide an enhanced AM-EWOD device. In some embodiments, the AM-EWOD device may form a part of a lab-on-a-chip system. Such devices may be used in manipulating, reacting and sensing chemical, biochemical or physiological materials. Applications include healthcare diagnostic testing, material testing, chemical or biochemical material synthesis, proteomics, tools for research in life sciences and forensic science.