8.

Preparation of a Positive Photoresist

Introduction This experiment involves the preparation of a solution inhibitor, 1-diazo-1,2naphthoquinone-5-sulfonate and subsequent use of this molecule in a simple positive photoresist. (expand this section a bit)
O N2 h? + N2 SO3 C8H1 7 aqueous base insoluble SO3 C8H1 7 SO3 C8H1 7 O O C H2O SO3 C8H1 7 aqueous base soluble O OH

Background and Theory Lithography is a technique used by the microelectronics industry in the fabrication of integrated circuits. In this context, the lithographic process involves using an exposure technique to transfer a pattern from a mask to a polymer film and finally to a semiconducting substrate. A variety of modes of exposure can be employed for this purpose including UV or X-ray radiation and electron- or ionbeams. The photolithographic process,1,2 whose main features appear in Figure 1-1, employs UV radiation and is the primary technique currently used in industrial applications. Briefly, a thin film (0.5 -10 ?m) of a photosensitive polymer, termed a resist, which has been spin-coated onto a semiconducting substrate is exposed to light through a mask. The mask is composed of a pattern which prevents light from reaching certain regions of the resist and allows it in other regions. Interaction of light with the resist induces a chemical change, creating a latent image of the pattern from the mask, in the resist. This photoinduced chemical change causes a difference in the dissolution rate between exposed and unexposed regions. Development of the resist with an appropriate solvent selectively dissolves the exposed or unexposed regions, producing positive or negative tone images, respectively. After the development step, regions of the substrate are left exposed, allowing them to be etched, thereby transferring the pattern to the substrate. Finally, the remaining resist is washed away to leave the bare, patterned substrate. Repetition of these steps with different masks and resists allows for the construction of detailed 3dimensional circuit patterns.

radiation mask photoresist substrate expose

latent image develop

etch

strip

positive image

negative image

The first positive resists were composed of a diazonaphthoquinone sensitizer as the PAC and a copolymer of variously substituted phenols with aldehydes, termed novolacs, as the polymer resin.1,5 In these positive resists, the exposed regions of the film become more soluble to an aqueous base developper than the unexposed regions. The solubility difference is derived from the fact that while novolacs are soluble in aqueous base, diazonaphthoquinones are not, and their presence in sufficient amounts inhibits solubilization of the resist prior to exposure. However, the main photoproduct of the diazonaphthoquinone is base soluble, thereby allowing solubilization of the resist after exposure to light. Upon absorption of a photon, the diazonaphthoquinone loses nitrogen to form a carbene which undergoes Wolff rearrangement to a ketene. The ketene is attacked by water to form an indenecarboxylic acid.

Equipment and Chemicals microscope slides, heavy-walled suction filtering flask, buchner funnel, filter paper, opaque stencil/mask, 2-diazo-1-naphthol-5-sulfonic acid sodium salt monohydrate, chlorosulfonic acid, 2-octanol, sodium bicarbonate, sodium hydroxide, novolak resin, petroleum ether, acetone, water Procedure Preparation of 1-diazo-1,2-naphthoquinone-5-sulfonate Caution-chlorosulfonic acid is corrosive and reacts violently with water Note- the entire procedure must be performed in subdued light to avoid premature initiation of the Wolff-rearrangement 1. Into a foil covered flask containing 3.0g of sodium 1-diazo-1,2naphthoquinone-5-sulfonate, carefully add chlorosulfonic acid (15 ml) so as to maintain the reaction temperature below 60C. 2. Heat the reaction mixture with gentle stirring for 15 min at 65-70C. The temperature should not be allowed to go above 75C in order to avoid thermal activation of the Wolff rearrangement. 3. Cool the flask in an ice bath. Add chilled deionized water (100 ml) dropwise down the thermometer such that the reaction temperature does not exceed 75C. Caution-the addition of water to chlorosulfonic acid is violently exothermic and liberates large quantities of gaseous HCl and concentrated H2SO4. 4. Collect the solid yellow precipitate and carefully dispose of the filtrate. 5. To the solid add 2-octanol (15 ml) and aqueous Na2CO3 (10%, 20 ml). 6. Gently stir the reaction mixture at room temperature for 90 minutes. 7. Chill the reaction mixture in an ice bath until a yellow solid forms (several minutes. 8. Collect the solid, wash it with cold water, air dry and wash with petroleum ether. 9. Dissolve a small amount in deuterated chloroform and obtain an H NMR. Then irradiate the solution in the NMR tube in the photoreactor until subsequent NMR spectra show formation of the indene-carboxylic acid. Preparation of the Photoresist 1. Dissolve the Novolak resin (0.5 g) in acetone (10 ml) with stirring. 2. Add 0.2 g of 1-diazo-1,2-naphthoquinone-5-sulfonate to the solution and continue stirring until the mixture is homogeneous. 3. Being careful to protect the solution from light, dip a microscope slide in a solution of the photoresist and allow it to dry in an oven at 60C for 30 minutes. It is important that all of the solvent be removed. 4. Place a mask (such as a key, coin, or photographic negative) over the photoresist and irradiate each slide in the photoreactor equipped with lamps in the ceiling for ? minutes. 5. Prepare 100 ml of developer solution: NaOH (?g) in 100 ml of water.

6. Dip and gently swirl an exposed slide in the developer solution adjusting the pH until dissolution times of about 4 minutes are achieved. 7. Rinse the slide in dilute acid (pH<5) to remove xs base and stop development reactions. 8. Repeat the exposure and development steps with other slides, varying both exposure time and development time to improve image resolution. Questions